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Electrochromic systems capable of switching absorption in the near‐infrared (NIR) region (750–2500 nm) are attractive from the viewpoint of applications for material and life science, and thus several examples have been reported to date. In general, the development of organic‐based systems is needed to reduce the environmental impact and improve biocompatibility. Although extending the switchable spectral range is crucial for the application of organic electrochromic molecules, the switching of NIR absorption based on redox interconversion is still a challenging issue regarding reversibility and durability during interconversion. To overcome this potential instability, the introduction of heteroatoms into the molecular backbone and/or π‐extension could be useful strategies in terms of effective delocalization of charge and spin in the corresponding redox states. In this review, we focus on redox‐active well‐defined small molecules that enable ON/OFF switching of NIR absorption based on precise control of the redox states, and present recent studies on their intrinsic electrochemical and spectroscopic properties and/or structural characterization of their charged states. [ABSTRACT FROM AUTHOR]

Hydride abstraction from the borane adduct, (BICAAC) ⋅ BH3 afforded the hydride bridged dinuclear borenium ion equivalent complexes 1 and 2 that have been characterized by various spectroscopic and spectrometric techniques followed by the assessment of Lewis acidity using the Gutmann‐Beckett method. The single crystal X‐ray structure of complex 2 revealed the presence of discrete ions in the solid state. The complex (BICAAC) ⋅ BH2(OTf) (3), obtained from the reaction of (BICAAC) ⋅ BH3 with MeOTf, formed the corresponding boronium cations [(BICAAC) ⋅ BH2(L)]+(OTf)− on reaction with Lewis bases (L= pyridine (4) and DMAP (5)). Complexes 1 and 2 demonstrated notable catalytic activity in the hydrosilylation of a diverse array of carbonyls using 1.0 mol % catalyst loading (achieving the highest turnover frequency (TOFmax) of up to 1200 h−1 with benzaldehyde. A broad substrate scope has been presented for aldehydes and ketones decorated with various electron‐donating and withdrawing substituents along with this the hydrosilylation of a few para‐quinone methides has also been presented. [ABSTRACT FROM AUTHOR]

The synthesis, characterization and reactivity of the diferrocenylphosphenium ion [Fc2P]+ was extended to the heavier diferrocenylpnictogenium ions, [Fc2E]+ (E=As, Sb, Bi). The lighter diferrocenylnitrenium ion, [Fc2N]+, was detected by mass spectrometry, but could not be isolated. The molecular structures of [Fc2E]+ (E=P, As, Sb, Bi) reveal intramolecular coordination of the iron atoms, which counterbalance the electron deficiency of the pnictogens without affecting the strong Lewis acidities, which were determined according to the method of Gutmann and Beckett. The (electro−)chemical oxidation and reduction afforded the dications [Fc2E]2+ (E=P (unstable), As) and the neutral dipnictogens Fc2EEFc2 (E=P, As). [ABSTRACT FROM AUTHOR]

Cyclophane‐type dications with two units of xanthylium were designed, with the expectation that intramolecular interaction between cation units could induce changes in absorption and redox behavior. The desired dications were synthesized via the macrocyclic diketone as a key intermediate, which was efficiently obtained by a stepwise etherification. X‐ray and UV/Vis measurements revealed that the cyclophane‐type dications adopt a stacking structure in both the crystal and solution. Due to the intramolecular interaction caused by π–π stacking of the xanthylium units, a considerable blue shift compared to the corresponding monocations and a two‐stage one‐electron reduction process were observed in the dications. Furthermore, upon electrochemical reduction of dications, the formation of biradicals via radical cation species was demonstrated by UV/Vis spectroscopy with several isosbestic points at both stages. Therefore, the cation‐stacking approach is a promising way to provide novel properties due to perturbation of their molecular orbitals and to stabilize the reduced species even though they have open‐shell characters. [ABSTRACT FROM AUTHOR]

Cation order, which can be controlled by synthesis conditions and stoichiometry, plays an important role in properties of perovskite materials. Here we show that aliovalent doping by Sb5+ in Sm2MnMn(Mn4−xSbx)O12 quadruple perovskite solid solutions can control cation orders in both A and B sites. Samples with 0.4≤x≤2 were synthesized by a high‐pressure, high‐temperature method at 6 GPa and 1770 K. Three regions with different cation orders were found at 0.5≤x≤1.0, x=1.5–1.6, and x=1.8. The 0.5≤x≤1.0 compositions have a B‐site‐disordered and A‐site columnar‐ordered structure with space group P42/nmc; the x=1.5 and 1.6 samples have a B‐site rock‐salt‐ordered and A‐site columnar‐ordered structure with space group P42/n; the x=1.8 sample has a B‐site rock‐salt‐ordered and A‐site‐disordered structure with space group P21/n. All the samples show one ferrimagnetic transition: TC increases from 35 K to 73 K for 0.5≤x≤1.0, TC=81 K for x=1.5 and 1.6, and TC=53 K for x=1.8. [ABSTRACT FROM AUTHOR]

The first example of a bis(cyaphido) complex, trans‐[Ru(dppe)2(C≡P)2], is described, unequivocally demonstrating the synthetic accessibility and stability of complexes that feature more than one cyaphido ligand. Synthesis is achieved from the precedent cation [Ru(dppe)2(C≡P)]+ via sequential coordination and desilylation of the phosphaalkyne Me3SiC≡P. The heteroleptic analogue trans‐[Ru(dppe)2(C≡N)(C≡P)] is also prepared from the same cation and NaCN; both cyaphido complexes are structurally characterized, enabling the first direct comparison of cyaphide with cyanide, its isoelectronic and isolobal counterpart. This demonstrates an enhanced π‐acidity for −C≡P over −C≡N, while computational studies reveal also a higher π‐donor character for the cyaphido ligand. [ABSTRACT FROM AUTHOR]

Cation order, which can be controlled by synthesis conditions and stoichiometry, plays an important role in properties of perovskite materials. Here we show that aliovalent doping by Sb5+ in Sm2MnMn(Mn4−xSbx)O12 quadruple perovskite solid solutions can control cation orders in both A and B sites. Samples with 0.4≤x≤2 were synthesized by a high‐pressure, high‐temperature method at 6 GPa and 1770 K. Three regions with different cation orders were found at 0.5≤x≤1.0, x=1.5–1.6, and x=1.8. The 0.5≤x≤1.0 compositions have a B‐site‐disordered and A‐site columnar‐ordered structure with space group P42/nmc; the x=1.5 and 1.6 samples have a B‐site rock‐salt‐ordered and A‐site columnar‐ordered structure with space group P42/n; the x=1.8 sample has a B‐site rock‐salt‐ordered and A‐site‐disordered structure with space group P21/n. All the samples show one ferrimagnetic transition: TC increases from 35 K to 73 K for 0.5≤x≤1.0, TC=81 K for x=1.5 and 1.6, and TC=53 K for x=1.8. [ABSTRACT FROM AUTHOR]

In the design of dynamic supramolecular systems used in molecular machines, it is important to understand the binding preferences between the macrocycle and stations along the thread. Here, we apply 1H NMR spectroscopy to investigate the relative stabilities of a series of linear alkylammonium templated pseudorotaxanes with the general formula [H2NRR'][Cr7CoF8(O2CCH2tBu)16] by exchanging the cation in solution. Our results show that the pseudorotaxanes are able to exchange threads via a dissociative mechanism. The position of equilibrium is dependent upon the ammonium cation and solvent used. Short chain primary ammonium cations are shown to be far less favourable macrocycle stations than secondary ammonium cations. Collision‐induced dissociation mass spectrometry (CID‐MS) has been used to look at disassembly of the pseudorotaxanes in a solvent‐free environment and stability trends compared to those in acetone‐d6. The energy needed to induce 50 % of the precursor ion loss (E50) is used and shows a similar trend to the equilibria measured by NMR. The relative stabilities of these hybrid inorganic‐organic pseudo‐rotaxanes are different to those of host‐guest compounds involving crown ethers and this may be valuable for the design of molecular machines. [ABSTRACT FROM AUTHOR]

Upon dibenzo annulation on Thiele's hydrocarbon (tetraphenyl‐p‐quinodimethane), the quinoid form and the biradical form adopt quite different geometries, and thus are no longer resonance structures. When these two forms can interconvert rapidly due to the small energy barrier (ΔG≠), the equilibrated mixture contains both forms in a ratio that is determined by the energy difference (ΔGo) between the two forms. For a series of tetrakis[5‐(4‐methoxyphenyl)‐2‐thienyl]‐substituted derivatives, the more stable quinoid form and the metastable biradical form coexist in solution as an equilibrated mixture due to small ΔG≠ (<15 kcal mol−1) and ΔGo (1–4 kcal mol−1), in which the proportion of the two forms can be regulated by temperature. Since the biradical form can undergo easy two‐electron (2e) oxidation to the corresponding dications as well as easy 2e‐reduction to the dianions, it exhibits very high electrochemical amphotericity. This character with a record‐small span for not only the first oxidation and reduction potentials but also the second those, [E1sum≈E2sum=E2ox−E2red=ca. 1.4 V], is attained through thermally enhanced conversion to the biradical form from the corresponding quinoid form, the latter of which is less amphoteric due to higher Eox and lower Ered values. [ABSTRACT FROM AUTHOR]

Owing to its high natural abundance compared to the commonly used transition (precious) metals, as well as its high Lewis acidity and ability to change oxidation state, aluminium has recently been explored as the basis for a range of single‐site catalysts. This paper aims to establish the ground rules for the development of a new type of cationic alkene oligomerisation catalyst containing two Al(III) ions, with the potential to act co‐operatively in stereoselective assembly. Five new dimers of the type [R2Al(2‐py′)]2 (R=Me, iBu; py′=substituted pyridyl group) with different substituents on the Al atoms and pyridyl rings have been synthesised. The formation of the undesired cis isomers can be suppressed by the presence of substituents on the 6‐position of the pyridyl ring due to steric congestion, with DFT calculations showing that the selection of the trans isomer is thermodynamically controlled. Calculations show that demethylation of the dimers [Me2Al(2‐py′)]2 with Ph3C+ to the cations [{MeAl(2‐py')}2(μ‐Me)]+ is highly favourable and that the desired trans disposition of the 2‐pyridyl ring units is influenced by steric effects. Preliminary experimental studies confirm that demethylation of [Me2Al(6‐MeO‐2‐py)]2 can be achieved using [Ph3C][B(C6F5)4]. [ABSTRACT FROM AUTHOR]

Heterocycles that pair main group elements and nitrogen are extremely important within the π‐conjugated heterocycles research community. Compared to the vast number of boron‐nitrogen heterocycles, those that include phosphorus are less common. Furthermore, the use of phosphorus‐nitrogen triple bonds of any type to prepare such compounds is unprecedented. Here, we pair pyridyl hydrazonide ligands with phosphadiazonium cations and demonstrate that the chelated Mes*NP group is directly implicated in the photophysical and redox properties observed for the resulting heterocycles. In doing so, we introduce a novel building block for the production of phosphorus‐containing heterocycles that could find use in small molecule activation and catalysis or as the functional component of emerging organic electronics. [ABSTRACT FROM AUTHOR]

Triphenylpnictogens EPh3 (E=N, P, As, Sb, Bi) are able to displace the perfluorinated Cp* ligand in [Rh(COD)(C5(CF3)5)] (COD=1,5‐cyclooctadiene) in up to quantitative yield. The resulting ionic products contain [C5(CF3)5]− as uncoordinated counter anion. The cations feature [Rh(COD)]+ fragments, coordinated by one (N, Bi), two (P, As) or three (Sb) triphenylpnictogen moieties. Whereas coordination via the pnictogen is observed for P, As and Sb, π‐coordination of the aryl rings is observed for N and Bi. [ABSTRACT FROM AUTHOR]

Partial ligand substitution at the iron pentacarbonyl radical cation generates novel half‐sandwich complexes of the type [Fe(η6‐arene)(CO)2]⋅+ (arene=1,3,5‐tri‐tert‐butylbenzene, 1,3,5‐trimethylbenzene, benzene and fluorobenzene). Of those, the bulkier 1,3,5‐tri‐tert‐butylbenzene (mes*) derivative [Fe(mes*)(CO)2]⋅+ was fully characterized by XRD analysis, IR, NMR, cw‐EPR, Mössbauer spectroscopy and cyclic voltammetry as the [Al(ORF)4]− (RF=C(CF3)3) salt. Chemical electronation, i. e. the single electron reduction, with decamethylferrocene generates neutral [Fe(mes*)(CO)2], whereas further deelectronation under CO‐pressure leads to a dicationic three‐legged [Fe(mes*)(CO)3]2+ salt with [Al(ORF)4]− counterion. The full substitution of the carbonyl ligands in [Fe(CO)5]⋅+[Al(ORF)4]− mainly resulted in disproportionation reactions, giving solid Fe(0) and the dicationic bis‐arene salts [Fe(η6‐arene)2]2+([Al(ORF)4]−)2 (arene=1,3,5‐trimethylbenzene, benzene and fluorobenzene). Only by employing the very large fluoride bridged anion [F‐{Al(ORF)3}2]−, it was possible to isolate an open shell bis‐arene cation salt [Fe(C6H6)2]⋅+[F‐{Al(ORF)3}2]−. The highly reactive cation was characterized by XRD analysis, cw‐EPR, Mössbauer spectroscopy and cyclic voltammetry. The disproportionation of [Fe(C6H6)2]⋅+ salts to give solid Fe(0) and [Fe(C6H6)2]2+ salts was analyzed by a suitable cycle, revealing that the thermodynamic driving force for the disproportionation is a function of the size of the anion used and the polarity of the solvent. [ABSTRACT FROM AUTHOR]

Seven pyridine iodine(I) sulfonate complexes were prepared and isolated at low temperatures and characterized by X‐ray diffraction analysis. The inherently instable pyridine iodine(I) cations are stabilized by an oxygen of sulfonate anions via the I⋅⋅⋅O halogen bond. In these complexes, the iodine atom of the pyridine iodine(I) cation acts as an electron acceptor and the sulfonate oxygen as the electron donor. These complexes are stable enough in the crystalline state, yet decompose rapidly under ambient conditions, also being unstable in solution. The (pyridine)N−I bond lengths [2.140(3)–2.197(2) Å] and the I⋅⋅⋅O halogen bonds [2.345(6)–2.227(3) Å] are analogous to (imide)N−I⋅⋅⋅O−N‐pyridine uncharged halogen‐bonded complexes formed from N‐haloimides and pyridine N‐oxides, thus confirming the existence of elusive pyridine iodine(I) cation. [ABSTRACT FROM AUTHOR]

Here we show that the sp‐hybridized nitrogen cation is strongly stabilized by a peri‐iodine substituent in the tetralone system. The cation is captured by anionic species such as CF3CO2−, affording hypervalent iodine(III) compounds with a short nitrogen‐iodine (N−I) bond, in which the cation serves as a Lewis acid. Notably, the O−I bond of the O‐trifluoroacetate or O‐acetate is intrinsically weaker than the N−I bond due to its more ionic character and is further weakened by protonation in trifluoroacetic acid. As a result, the oxygen ligand can dissociate in the presence of a Brønsted acid, affording a I+ cation intermediate that retains the N−I bond. We isolated the cation as the tetrafluoroborate, and characterized it experimentally by 1H NMR spectroscopy and X‐ray structure analysis, and theoretically by means of DFT calculation. The results suggest that the N−I bonded cation is intrinsically stable, and is weakly coordinated with water and the BF4 counter anion or trifluoroacetate anion. This cation can be employed as a reagent for α‐oxidation of ketones. [ABSTRACT FROM AUTHOR]

A new series of unsymmetrical phenyl tellurides derived from 2‐N‐(quinolin‐8‐yl) benzamide ligand has been synthesized in a practical manner by the copper‐catalyzed method by using diaryl ditelluride and Mg as a reductant at room temperature. In order to augment the Lewis acidity of these newly formed unsymmetrical monotellurides, these have been transformed into corresponding unsymmetrical 2‐N‐(quinolin‐8‐yl)benzamide tellurium cations. Subsequently, these Lewis acidic tellurium cations were used as chalcogen bonding catalysts, enabling the synthesis of various substituted 1,2‐dihydroquinolines by activating ketones with anilines under mild conditions. Moreover, the synthesized 2‐N‐(quinolin‐8‐yl)benzamide phenyl tellurium cation has also catalyzed the formation of β‐amino alcohols in high regioselectivity by effectively activating epoxides at room temperature. Mechanistic insight by 1H and 19F NMR study, electrostatic surface potential (ESP map), control reaction in which tellurium cation reacted explosively with epoxide, suggested that the enhanced Lewis acidity of tellurium center seems responsible for efficient catalytic activities under mild conditions enabling β‐amino alcohols with excellent regioselectivity and 1,2‐dihydroquinolines with trifluoromethyl, nitro, and pyridylsubstitution, which were difficult to access. [ABSTRACT FROM AUTHOR]

In recent years, the thermochromic hydrogel was acted as suitable sandwiching material to adjust light transmission. However, to accurately control the thermochromic temperature in a wide range still was a significant challenge. Here, a simple method was explored to prepare hydrogels with gradient opaque‐transparent transition thermochromic temperature from 5 °C to 53 °C, which was regulated by the aggregation state of sodium dodecyl sulfate micelles by adding potassium tartrate hemihydrate and cations. Using Li+, Na+, and K+ as cations, the accuracy was controlled at 1 °C. Moreover, the transmittance of the hydrogel was not changed when the thermochromic temperature was adjusted. As a result, an intelligent window was fabricated by utilizing thermochromic hydrogel as a sandwiching layer into the outer glass layers, which could effectively and stably regulate the visible and infrared light. The temperature monitors/detectors were also designed, which showed excellent temperature monitoring/detecting ability. Therefore, this low‐cost, high‐efficient, large‐scale prepared thermochromic hydrogel provided more potential for intelligent temperature devices. [ABSTRACT FROM AUTHOR]

Recently, chalcogen bond catalysts with telluronium cations have garnered considerable attention in organic reactions. In this work, chalcogen bond catalysis on the bromination reaction of anisole with N‐bromosuccinimide (NBS) with the telluronium cationic catalysts has been explored with density functional theory (DFT). The catalytic reaction is divided into two stages: the bromine transfer step and the proton transfer step. Based on the computational results, one can find the rate‐determining step is the bromine transfer step. Moreover, the present study elucidates that a stronger chalcogen bond between catalysts and NBS will give better catalytic performance. Additionally, this work also clarified the importance of the electrostatic and polarization effects in the chalcogen bond between the oxygen atom of NBS and the Te atom of the catalyst in this bromination reaction. The electrostatic and polarization effects are significantly influenced by the electron‐withdrawing ability of the substitution groups on the catalysts. Moreover, the structure‐property relationship between the strength of chalcogen bond, electrostatic effect, polarization effect and catalytic performance are established for the design of more efficient chalcogen bond catalysts. [ABSTRACT FROM AUTHOR]

The chemistry of alkali‐metal enolates is dominated by ion pairing. To improve our understanding of the intrinsic interactions between the alkali‐metal cations and the enolate anions, we have applied Cooks' kinetic method to determine relative M+ (M=Li, Na, K) affinities of the stabilized enolates derived from acetylacetone, ethyl acetoacetate, diethyl malonate, ethyl cyanoacetate, 2‐cyanoacetamide, and methyl malonate monoamide in the gas phase. Quantum chemical calculations support the experimental results and moreover afford insight into the structures of the alkali‐metal enolate complexes. The affinities decrease with increasing size of the alkali‐metal cations, reflecting weaker electrostatic interactions and lower charge densities of the free M+ ions. For the different enolates, a comparison of their coordinating abilities is complicated by the fact that some of the free anions undergo conformational changes resulting in stabilizing intramolecular interactions. If these complicating effects are disregarded, the M+ affinities correlate with the electron density of the chelating functionalities, that is, the carbonyl and/or the nitrile groups of the enolates. A comparison with the known association constants of the corresponding alkali‐metal enolates in solution points to the importance of solvation effects for these systems. [ABSTRACT FROM AUTHOR]

The dinuclear bis(N‐heterocyclic carbene) borane adduct 2 rapidly reacts with tritylium salts at room temperature but the outcome is strongly impacted by the respective counter‐ion. Using tritylium tetrakis(perfluoro‐tert‐butoxy)aluminate affords – depending on the solvent – either the bis(boronium) ion 4 or the hydride‐bridged dication 5. In case of tritylium hexafluorophosphate, however, H/F exchange occurs between boron and phosphorus yielding the dinuclear BF3 adduct 3 along with phosphorus dihydride trifluoride. H/F exchange also takes place when using the mononuclear N‐heterocyclic carbene BH3 adduct 6 and hence provides a facile route to PH2F3, which is usually synthesized in more complex reaction sequences regularly involving toxic hydrogen fluoride. DFT calculations shed light on the H/F exchange between the borenium ion and the [PF6]− counter‐ion and the computed mechanism features only small barriers in line with the experimental observations. [ABSTRACT FROM AUTHOR]

Although the discovery of the GaI complex salt [Ga(PhF)2‐3][Al(ORF)4] (RF=C(CF3)3, PhF=C6H5F) invoked the preparation of a diverse library of cationic Ga(I) coordination complexes and clusters, studies on small molecule activation with low‐valent GaI cations are scarce. Herein, a first experimental study on the reactivity of a monomeric Ga(I) cation activated with a pyridine–diimine pincer ligand (in [Ga(PDIdipp)][Al(ORF)4]) towards small‐molecules is reported. First controlled oxidative additions of the GaI cation into C−Cl, H−P and P−P bonds are presented. Moreover, the [4+1]cycloaddition to butadienes was achieved. Intriguingly, the isolated, blue insertion product into the P−P bond of P4 allows for the quantitative release of the P4 molecule upon reaction with AlEt3 and butadienes. Reversible P4 insertion of main‐group metals has previously been reported for Ge and Sn, respectively. The experimental study is supported by high‐level computational analysis of the in‐part reversible oxidative additions at the DLPNO‐CCSD(T)/def2‐TZVPP//PBEh‐3c/def2‐mSVP level of theory with COSMO‐RS solvation in 1,2‐difluorobenzene. [ABSTRACT FROM AUTHOR]

Strong Lewis acids are essential tools for manifold chemical procedures, but their scalable deployment is limited by their costs and safety concerns. We report a scalable, convenient, and inexpensive synthesis of stable diiminium‐based reagents with a Lewis acidic carbon centre. Coordination with pyridine donors stabilises these centres; the 2,2'‐bipyridine adduct shows a chelation effect at carbon. Due to high fluoride, hydride, and oxide affinities, the diiminium pyridine adducts are promising soft and hard Lewis acids. They effectively produce acylpyridinium salts from carboxylates that can acylate amines to give amides and imides even from electronically intractable coupling partners. [ABSTRACT FROM AUTHOR]

Although the discovery of the GaI complex salt [Ga(PhF)2‐3][Al(ORF)4] (RF=C(CF3)3, PhF=C6H5F) invoked the preparation of a diverse library of cationic Ga(I) coordination complexes and clusters, studies on small molecule activation with low‐valent GaI cations are scarce. Herein, a first experimental study on the reactivity of a monomeric Ga(I) cation activated with a pyridine–diimine pincer ligand (in [Ga(PDIdipp)][Al(ORF)4]) towards small‐molecules is reported. First controlled oxidative additions of the GaI cation into C−Cl, H−P and P−P bonds are presented. Moreover, the [4+1]cycloaddition to butadienes was achieved. Intriguingly, the isolated, blue insertion product into the P−P bond of P4 allows for the quantitative release of the P4 molecule upon reaction with AlEt3 and butadienes. Reversible P4 insertion of main‐group metals has previously been reported for Ge and Sn, respectively. The experimental study is supported by high‐level computational analysis of the in‐part reversible oxidative additions at the DLPNO‐CCSD(T)/def2‐TZVPP//PBEh‐3c/def2‐mSVP level of theory with COSMO‐RS solvation in 1,2‐difluorobenzene. [ABSTRACT FROM AUTHOR]

Most redox systems generally cannot avoid the involvement of open‐shell species upon generating multiply charged species, which often reduces reversibility in multi‐color electrochromic systems. In this study, we newly synthesized octakis(aminophenyl)‐substituted pentacenebisquinodimethane (BQD) derivatives and their hybrids with alkoxyphenyl analogues. Thanks to apparent two‐electron transfer accompanied by double dramatic changes in the structure of the arylated quinodimethane skeleton, the dicationic and tetracationic states were generated and isolated quantitatively because of the negligible steady‐state concentration of intermediary open‐shell species such as monocation or trication radicals. When two electrophores with different donating abilities are attached to the BQD skeleton, a dicationic state with a different color can be isolated in addition to the neutral and tetracationic states. For these tetracations, an interchromophore interaction induces a red‐shift of the NIR absorptions, thus realizing tricolor UV/Vis/NIR electrochromic behavior involving only closed‐shell states. [ABSTRACT FROM AUTHOR]

A nitrogen‐centered heptalene, azaheptalene, was designed as a representative of a new class of redox‐responsive molecules with a large steric strain that originates from the adjacent seven‐membered rings. The pentabenzo derivative of azaheptalene was efficiently synthesized by a palladium‐catalyzed one‐pot reaction of commercially available reagents. Bromination led to mono‐ and dibrominated derivatives, the latter of which is interconvertible with isolable radical cation species exhibiting near‐infrared absorption. Since the azaheptalene skeleton shows configurationally stable helicity with a large torsion angle, enantiomers could be successfully separated. Thus, optically pure azaheptalenes with P‐ or M‐helicity showed strong chiroptical properties (|gabs|≥0.01), which could be changed by an electric potential. [ABSTRACT FROM AUTHOR]

The unsubstituted acenium radical cations (ARCs) are extremely sensitive and were hitherto only studied in situ, i. e. in the gas phase, as dilute solutions in strong acids or by matrix isolation spectroscopy at about 10 K. In this study, room temperature stable ARC salts with the weakly coordinating anion [F{Al(ORF)3}2]− (ORF=−OC(CF3)3) supported by the weakly coordinating solvent 1,2,3,4‐tetrafluorobenzene (TFB) were prepared and structurally, electrochemically and spectroscopically characterized. Reaction of the neutral acenes with Ag+[F{Al(ORF)3}2]− led, non‐innocent,[54] to intermediate [Ag2(acene)2]2+ complexes, which decompose over time to Ag0 and the corresponding (impure) ARC salts. By contrast, direct deelectronation with the recently developed innocent[54] deelectronator radical cation salt [anthraceneHal]+⋅[F{Al(ORF)3}2]− led to phase‐pure products [acene]+⋅[F{Al(ORF)3}2]− (anthraceneHal=9,10‐dichlorooctafluoroanthracene; acene=anthra‐, tetra‐, pentacene). For the first time, a homogenous set of spectroscopic data on analytically pure ARC salts was obtained. In addition, cyclovoltammetric measurements of the acenes connected the potentials in solution with those in the gas‐phase. Hence, the data complement the existing isolated gas‐phase, strong acid or matrix isolation studies. A first entry to follow‐up chemistry of the acenium radical cations as ligand forming oxidizers was demonstrated by reaction with 1/2 ${{ 1/2 }}$ Co2(CO)8 giving [Co(anthracene)(CO)2]+. [ABSTRACT FROM AUTHOR]

Ions appear as active components in diverse materials. Here, the bonding energy between mechanically interlocked molecules (MIMs) or their acyclic/cyclic molecular derivatives and i) Cl− and Br− ions and/or ii) Na+ and K+ ions, have been investigated. The chemical environment provided by MIMs is less preferably to recognize ionic species compared to unconstrained interactions that are furnished by acyclic molecules. However, MIMs can be more adequate structures for ionic recognition than cyclic compounds if a chemical arrangement of the bond sites that relevantly support more favorable interactions with ions compared to Pauli repulsive ambient is provided. The hydrogen replacement by electron donor (−NH2) or acceptor (−NO2) groups in MIMs favors the anion/cation recognition due to decreased Pauli repulsion energy and/or more attractive non‐covalent bonds. This study clarifies the chemical environment provided by MIMs to interact with ions and highlights these molecules as relevant structures to realize ionic sensing. [ABSTRACT FROM AUTHOR]

The stable, easily accessible salt [Ni(CO)4]+[F{Al(ORF)3}2]− (RF=C(CF3)3) was used as a NiI synthon to generate the novel half‐sandwich complexes [Ni(arene)(CO)2]+ (arene=C6H6, o‐dfb=1,2‐F2C6H4). By irreversible removal of CO from the equilibrium, even the rather endergonic reaction to a [Ni(o‐dfb)2]+ salt was successful (ΔrG°(solv)=+78 kJ mol−1). The latter displays an unprecedented slipped η3,η3‐sandwich structure and is the ultimate synthon to NiI‐chemistry. [ABSTRACT FROM AUTHOR]

Electrochromic systems capable of switching near‐infrared (NIR) absorption are fascinating from the viewpoint of applications in the materials and life sciences. Although 11,11,12,12‐tetraaryl‐9,10‐anthraquinodimethanes (AQDs) with a folded form undergo one‐stage two‐electron oxidation to produce twisted dicationic dyes exhibiting NIR absorption, there is a need to establish a design strategy that can enhance the NIR‐absorbing abilities of the corresponding dicationic dyes. In this study, we designed and synthesized a series of AQD derivatives with various substituents introduced at the ortho‐position(s) of the 4‐methoxyphenyl group. X‐ray and spectroscopic analyses revealed that NIR‐absorbing properties can be changed by introduction of the ortho‐substituents. Thus, control of the steric and electronic effects of the ortho‐substituents on the 4‐methoxyphenyl groups was demonstrated to be an effective strategy for fine‐tuning of the HOMO and LUMO levels for neutral AQDs and twisted dications, respectively, resulting in the modification of electrochemical and spectroscopic properties under an "ortho‐substitution strategy". [ABSTRACT FROM AUTHOR]

In switchable molecular recognition, 1O2 stimulus responsive receptors offer a unique structural change that is rarely exploited. The employed [4+2] reaction between 1O2 and anthracene derivatives is quantitative, reversible and easily implemented. To evaluate the full potential of this new stimulus, a non‐macrocyclic anthracene‐based host was designed for the modular binding of cations. The structural investigation showed that 1O2 controlled the atropisomerism in an on/off fashion within the pair of hosts. The binding studies revealed higher association constants for the endoperoxide receptor compared to the parent anthracene, due to a more favoured preorganization of the recognition site. The fatigue of the 1O2 switchable hosts and their complexes was monitored over five cycles of cycloaddition/cycloreversion. [ABSTRACT FROM AUTHOR]

Understanding molecular‐scale reaction mechanisms is crucial for the design of modern catalysts with industrial prospect. Through joint experimental and computational studies, we investigate the direct coupling reaction of CH4 and CO2, two abundant greenhouse gases, mediated by Ta1,4+ ions to form larger oxygenated hydrocarbons. Coherent with proposed elementary steps, we expose products of CH4 dehydrogenation [Ta1,4CH2]+ to CO2 in a ring electrode ion trap. Product analysis and reaction kinetics indicate a predisposition of the tetramers for C−O coupling with a conversion to products of CH2O, whereas atomic cations enable C−C coupling yielding CH2CO. Selected experimental findings are supported by thermodynamic computations, connecting structure, electronic properties, and catalyst function. Moreover, the study of bare Ta1,4+ compounds indicates that methane dehydrogenation is a significant initial step in the direct coupling reaction, enabling new, yet unknown reaction pathways. [ABSTRACT FROM AUTHOR]

Recently, it was shown that the double Ca−H−Ca bridged calcium hydride cation dimer complex [LCaH2CaL]2+ (macrocyclic ligand L=NNNN‐tetradentate Me4TACD) exhibited remarkable activity in catalyzing the hydrogenation of unactivated 1‐alkenes as well as the H2 isotope exchange under mild conditions, tentatively via the terminal Ca−H bond of cation monomer LCaH+. In this DFT mechanistic work, a novel substrate‐dependent catalytic mechanism is disclosed involving cooperative Ca−H−Ca bridges for H2 isotope exchange, competitive Ca−H−Ca bridges and terminal Ca−H bonds for anti‐Markovnikov addition of unactivated 1‐alkenes, and terminal Ca−H bonds for Markovnikov addition of conjugation‐activated styrene. THF‐coordination plays a key role in favoring the anti‐Markovnikov addition while strong cation‐π interactions direct the Markovnikov addition to terminal Ca−H bonds. [ABSTRACT FROM AUTHOR]

10,11‐Bis[bis(4‐dimethylaminophenyl)methylene]dibenzo[bf]thiepin (1) and ‐oxepin (2) were prepared as stable yellow crystalline compounds, which are the cyclic analogues of electron‐donating hexaarylbutadienes. Upon two‐electron oxidation, they are reversibly transformed into the title dications (12+ and 22+) exhibiting near‐infrared (NIR) absorptions, which were also isolated as stable salts. These redox pairs can serve as new entries into less well‐explored organic NIR‐electrochromic systems, and the separation of redox peaks (electrochemical bistability) was attained for 1/12+ and 2/22+, thanks to drastic geometrical changes between neutral and dicationic states, as revealed by a series of X‐ray analyses. Thiepin‐S,S‐dioxide analogue (3/32+) exhibits quite similar dynamic redox behavior due to nonaromatic nature of the dibenzothiepin and ‐oxepin unit in 12+ and 22+, whereas the thiepin‐S‐oxide derivative (4/42+) does not exhibit bistability due to the smaller change in geometry upon electron transfer, showing that a subtle change of a bridging atom in the central seven‐membered ring can modify the redox properties. [ABSTRACT FROM AUTHOR]

In this work, the modulation of activity and selectivity via photoreduction of carbon dioxide under simulated sunlight was achieved by treating P25 and P25/Pt NPs with KOH. It found that KOH treatment could significantly improve the overall conversion efficiency and switch the selectivity for CO. Photoelectric characterizations and CO2‐TPD demonstrated that the synergistic effect of K+ and OH‐ accelerated the separation and migration of photogenerated charges, and also improved CO2 adsorption level. Significantly, the K ions could act as active sites for CO2 adsorption and further activation. In situ FTIR measurements and DFT calculations confirmed that K+ enhanced the charge density of adjacent atoms and stabilize CO* groups, reducing the reaction energy barrier and inducing the switching of original CH4 to CO, which played a selective regulatory role. This study provides insights into the photocatalytic activity and selectivity of alkali‐treated photocatalysts and facilitates the design of efficient and product‐specific photocatalysis. [ABSTRACT FROM AUTHOR]

Hydrochromic materials, which change color in response to moisture, are highly sought‐after due to some unique applications such as moisture detection, humidity monitoring, anti‐counterfeiting, and sweat‐pore mapping. We herein report a new thioxanthene‐9‐ols/thioxanthylium cations hydrochromic system. The hydrochromic thioxanthylium cations can be generated/regenerated by exposing a chemically stable thioxanthene‐9‐ol to trifluoroacetic acid (TFA). The intensely colored thioxanthylium cations can be chemically reverted to the colorless thioxanthene‐9‐ol. Interestingly, the conversion between thioxanthene‐9‐ol and its cation species was found to be highly reversible in most cases (up to 50 activation‐deactivation cycles). The color and moisture‐sensitivity of thioxanthylium cations were also validated to be tunable via functionalization of the thioxanthene core with different aliphatic and aromatic groups at its 9 or 2,7‐positions. Finally, paper probes were prepared using solution‐immersion and inkjet‐printing techniques to demonstrate the system's potential applications in humidity sensing and anti‐counterfeiting [ABSTRACT FROM AUTHOR]

Uronic acids are carbohydrates carrying a terminal carboxylic acid and have a unique reactivity in stereoselective glycosylation reactions. Herein, the competing intramolecular stabilization of uronic acid cations by the C‐5 carboxylic acid or the C‐4 acetyl group was studied with infrared ion spectroscopy (IRIS). IRIS reveals that a mixture of bridged ions is formed, in which the mixture is driven towards the C‐1,C‐5 dioxolanium ion when the C‐5,C‐2‐relationship is cis, and towards the formation of the C‐1,C‐4 dioxepanium ion when this relation is trans. Isomer‐population analysis and interconversion barrier computations show that the two bridged structures are not in dynamic equilibrium and that their ratio parallels the density functional theory computed stability of the structures. These studies reveal how the intrinsic interplay of the different functional groups influences the formation of the different regioisomeric products. [ABSTRACT FROM AUTHOR]

The coordination and redox chemistry of aqueous CeIV/III macrocyclic compounds were studied by using the ligands DOTA and DOTP (1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetrayl)tetraacetic acid and 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetra(methylene phosphonic acid), respectively). The hydrolysis tendency of the tetravalent cation in the presence of DOTA is shown to result in the formation of a highly ordered, fluorite‐like [CeIV6(O)4(OH)4(H2O)8(DOTAH)4] oxo‐hydroxo structure both in solution and in the solid state. The lifetime of the analogous species formed in the presence of DOTP was found to be much shorter. Spectroscopic measurements of the latter suggest its similarity to the former. Its gradual decomposition in solution leads to the accumulation of the in‐cage complexes [CeIVDOTP] and [CeIIIDOTP(H2O)], which were crystallographically characterized in this study. The redox energetics and spectroscopic characteristics for the transition between these two in‐cage complexes in aqueous solutions were studied as well. Together with the crystallographic structures of the above‐mentioned species, the in‐cage [CeIVDOTA(H2O)] complex structure is presented herein for the first time. An elaborative analysis of the X‐ray crystallographic structural data obtained for the in‐cage complexes studied herein and similar structures published previously suggests that hard‐bonding cyclen‐derived ligands are, counter‐intuitively, better suited for encapsulating, and perhaps kinetically stabilize softer cations than harder ones with DOTP, marked as a possible adequate chelator for the study of the aqueous properties of LnII and AcIII cations. [ABSTRACT FROM AUTHOR]

Molybdenum(VI) bis(imido) complexes [Mo(NtBu)2(LR)2] (R=H 1 a; R=CF31 b) combined with B(C6F5)3 (1 a/B(C6F5)3, 1 b/B(C6F5)3) exhibit a frustrated Lewis pair (FLP) character that can heterolytically split H−H, Si−H and O−H bonds. Cleavage of H2 and Et3SiH affords ion pairs [Mo(NtBu)(NHtBu)(LR)2][HB(C6F5)3] (R=H 2 a; R=CF32 b) composed of a Mo(VI) amido imido cation and a hydridoborate anion, while reaction with H2O leads to [Mo(NtBu)(NHtBu)(LR)2][(HO)B(C6F5)3] (R=H 3 a; R=CF33 b). Ion pairs 2 a and 2 b are catalysts for the hydrosilylation of aldehydes with triethylsilane, with 2 b being more active than 2 a. Mechanistic elucidation revealed insertion of the aldehyde into the B−H bond of [HB(C6F5)3]−. We were able to isolate and fully characterize, including by single‐crystal X‐ray diffraction analysis, the inserted products Mo(NtBu)(NHtBu)(LR)2][{PhCH2O}B(C6F5)3] (R=H 4 a; R=CF34 b). Catalysis occurs at [HB(C6F5)3]− while [Mo(NtBu)(NHtBu)(LR)2]+ (R=H or CF3) act as the cationic counterions. However, the striking difference in reactivity gives ample evidence that molybdenum cations behave as weakly coordinating cations (WCC). [ABSTRACT FROM AUTHOR]

Por‐crownphyrin‐art: Crownphyrinoids—hybrid macrocycles comprising crown ethers and porphyrin functionalities—show versatile coordination properties and reactivity. Depending on the oxidation level of the macrocycle and the type of metal cation, they form several structures resulting from binding one or two metal centres. More information can be found in the Research Article by B. Szyszko and co‐workers (DOI: 10.1002/chem.202402932). Artwork created by M.M...By Maksym Matviyishyn; Krzysztof A. Konieczny; Bartosz Trzaskowski and Bartosz SzyszkoReported by Author; Author; Author; Author [Extracted from the article]

The Cover Feature illustrates defects in the NaGa4 structure caused by the mutual exchange of Na atoms and Ga₂ dumbbells. These defects form at elevated temperatures and can be interpreted as the embedding of CeMg2Si2‐type segments into the BaAl4‐type matrix. More information can be found in the Research Article by Y. Grin and co‐workers (DOI: 10.1002/chem.202402457)...By Chia‐Chi Yu; Yurii Prots; Primož Koželj; Frank R. Wagner; Michael Baitinger and Yuri GrinReported by Author; Author; Author; Author; Author; Author [Extracted from the article]

The article titled "Cover Feature: Ion-Pairing Assemblies of Anion-Responsive π-Electronic Systems That Have Noncovalently Assisted Expanded Planar Region" discusses the properties of arylethynyl‐substituted dipyrrolyldiketone BF2 complexes as anion-responsive π-electronic molecules. These molecules exhibit enhanced one-photon absorption and two-photon absorption when anions bind to them, due to conformation changes. The anion complexes form solid-state charge-by-charge ion-pairing assemblies with π-electronic cations, facilitated by intramolecular interactions. The article provides more detailed information on this research. [Extracted from the article]

Visualization of cation dynamics inside a living system represent a major breakthrough at the crossroad of chemistry and cellular physiology. Since the inception of BAPTA‐based cellular calcium indicators in the 1980s, generations of chemical and genetically encoded ion indicators spanning the visible spectrum have been developed. In this article, we bring up three emerging concepts in this field: 1. red‐shifting cation indicators towards far‐red and near‐infrared (NIR) channels; 2. directing the indicators to various subcellular localizations; 3. lowering the phototoxicity of indicators for long term recording. These initiatives collectively echo the advocate of 4D cellular physiology, where biological processes within living systems can be panoramically unveiled under 3D, long‐term, and multi‐channel imaging with unprecedented spatial and temporal resolution. This outlook poses exciting challenges and opportunities for chemists to upgrade the toolkit of fluorescent indicators as key enablers for a new era of imageomics. [ABSTRACT FROM AUTHOR]

The present review focuses on recent examples of tetracoordinate boryl groups greatly influencing reactions in organic synthesis. Electron‐rich tetracoordinate boryl groups stabilize or activate reactive intermediates such as cations, radicals and π‐conjugation systems, and interaction of the intermediates with carbon‐boron or heteroatom‐boron bonds is the origin of such substituent effects. Unique substituent effects of tetracoordinate boryl groups often promote desired reactions and affect results of reactions such as yield and selectivity of products. [ABSTRACT FROM AUTHOR]

Arylmethyl anions allow alkali‐metals to bind in a σ‐fashion to the lateral carbanionic centre or a π‐fashion to the aryl ring or in between these extremities, with the trend towards π bonding increasing on descending group 1. Here we review known alkali metal structures of diphenylmethane, fluorene, 2‐benzylpyridine and 4‐benzylpyridine. Next, we synthesise Li, Na, K monomers of these diarylmethyls using polydentate donors PMDETA or Me6TREN to remove competing oligomerizing interactions, studying the effect that two aromatic rings has on negative charge (de)localisation via NMR, X‐ray crystallographic and DFT studies. Diphenylmethyl and fluorenyl anions maintain C(H)−M interactions regardless of alkali‐metal, although the adjacent arene carbons engage in interactions with larger alkali‐metals. Introducing a nitrogen atom into the ring (at the 2‐ or 4‐position) encourages relocalisation of negative charge away from the deprotonated carbon and onto nitrogen. Phenyl(2‐pyridyl)methyl moves from an enamide formation at one extremity (lithium) to an aza‐allyl formation at the other extremity (potassium), while C‐ or N‐coordination modes become energetically viable for Na and K phenyl(4‐pyridyl)methyl complexes. [ABSTRACT FROM AUTHOR]

Surface electric field of catalyst is widely recognized as one of the key points to boost catalytic activity. However, there is still a lack of convenient ways to tune the surface electric field to selectively boost the catalytic conversions of different types of reactants in specific catalytic reactions. Here, we introduce a conceptually new method to tune the surface electric field of electrode materials by adjusting the number and density of heterojunctions inside. Both theoretical and experimental results prove that the well‐designed surface electric field of an electrocatalyst plays a key role in facilitating pre‐adsorption and/or activation of reactants for selective conversion of trash ions to useful products in hydrogen and oxygen evolution reactions as well as NOx− reduction reactions. [ABSTRACT FROM AUTHOR]

A new series of lanthanide (1–5) and uranyl (6) complexes with a tetra‐substituted bifunctional calixarene ligand H2L is described. The coordination environment for the Ln3+ and UO22+ ions is provided by phosphoryl and salicylamide functional groups appended to the lower rim of the p‐tert‐butylcalix[4]arene scaffold. Ligand interactions with lanthanide cations (light: La3+, Pr3+; intermediate: Eu3+ and Gd3+; and heavy: Yb3+), as well as the uranyl cation (UO22+) is examined in the solution and solid state, respectively with spectrophotometric titration and single crystal X‐ray diffractometry. The ligand is fully deprotonated in the complexation of trivalent lanthanide ions forming di‐cationic complexes 2 : 2 M : L, [Ln2(L)2(H2O)]2+ (1–5), in solution, whereas uranyl formed a 1 : 1 M : L complex [UO2(L)(MeOH)]∞ (6) that demonstrated very limited solubility in 12 organic solvents. Solvent extraction behaviour is examined for cation selectivity and extraction efficiency. H2L was found to be an effective extracting agent for UO22+ over La3+ and Yb3+ cations. The separation factors at pH 6.0 are: βUO22+/La3+ =121.0 and βUO22+/Yb3+ =70.0. [ABSTRACT FROM AUTHOR]

The enhancement mechanism of birefringence is very important to modulate optical anisotropy and materials design. Herein, the different cations extending from alkaline‐earth to alkaline‐earth, d10 electron configuration, and 6s2 lone pair cations are highlighted to explore the influence on the birefringence. A flexible fluorooxoborate framework from AEB4O6F2 (AE=Ca, Sr) is adopted for UV/deep‐UV birefringent structures, namely, MIIB4O6F2 (MII=Be, Mg, Pb, Zn, Cd). The maximal enhancement on birefringence can reach 46.6 % with the cation substitution from Ca, Sr to Be, Mg (route‐I), Pb (route‐II), and Zn, Cd (route‐III). The influence of the cation size, the stereochemically active lone pair, and the binding capability of metal cation polyhedra is investigated for the hierarchical improvement on birefringence. Significantly, the BeB4O6F2 structure features the shortest UV cutoff edge 146 nm among the available anhydrous beryllium borates with birefringence over 0.1 at 1064 nm, and the PbB4O6F2 structure has the shortest UV cutoff edge 194 nm within the reported anhydrous lead borates that hold birefringence larger than 0.1 at 1064 nm. This work sheds light on how metal cation polyhedra modulate birefringence, which suggests a credible design strategy to obtain desirable birefringent structures by cation control. [ABSTRACT FROM AUTHOR]

Although N‐heterocyclic phosphenium (NHP) cations have received considerable research interest due to their application in organocatalysis, including asymmetric synthesis, phosphenium cations with other substitution patterns have hardly been explored. Herein, the preparation of a series of ylide‐substituted cations of type [YPR]+ (with Y=Ph3PC(Ph), R=Ph, Cy or Y) and their structural and coordination properties are reported. Although the diylide‐substituted cation forms spontaneous from the chlorophosphine precursor, the monoylidylphosphenium ions required the addition of a halide‐abstraction reagent. The molecular structures of the cations reflected the different degrees of electron donation from the ylide to the phosphorus center depending on the second substituent. Molecular orbital analysis confirmed the stronger donor properties of the ylide systems compared to NHPs with the mono‐ylide substituted cations featuring a more pronounced electrophilicity. This was mirrored by the reaction of the cations towards gold chloride, in which only the diylide‐substituted cation [Y2P]+ formed the expected LAuCl]+ complex, while the monoylide‐substituted compounds reacted to the chlorophosphine ligands by transfer of the chloride from gold to the phosphorus center. These results demonstrate the tunability of ylide‐functionalized phosphorus cations, which should allow for further applications in coordination chemistry in the future. [ABSTRACT FROM AUTHOR]

Elemental tellurium readily dissolves in ionic liquids (ILs) based on tetraalkylphosphonium cations even at temperatures below 100 °C. In the case of ILs with acetate, decanoate, or dicyanamide anions, dark red to purple colored solutions form. A study combining NMR, UV‐Vis and Raman spectroscopy revealed the formation of tellurium anions (Ten)2− with chain lengths up to at least n=5, which are in dynamic equilibrium with each other. Since external influences could be excluded and no evidence of an ionic liquid reaction was found, disproportionation of the tellurium is the only possible dissolution mechanism. Although the spectroscopic detection of tellurium cations in these solutions is difficult, the coexistence of tellurium cations, such as (Te4)2+ and (Te6)4+, and tellurium anions could be proven by cyclic voltammetry and electrodeposition experiments. DFT calculations indicate that electrostatic interactions with the ions of the ILs are sufficient to stabilize both types of tellurium ions in solution. [ABSTRACT FROM AUTHOR]

The synthesis, characterization and reactivity studies of the NHC‐stabilized complex IDipp ⋅ GeH2BH2OTf (1) (IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) are reported. Nucleophilic substitution of the triflate (OTf) group in 1 by phosphine or arsine donors provides access to the cationic group 13/14/15 chains [IDipp ⋅ GeH2BH2ERR1R2]+ (2 E=P; R, R1=H; R2=tBu; 3 E=P; R=H; R1, R2=Ph; 4 a E=P; R, R1, R2=Ph; 4 b E=As; R, R1, R2=Ph). These novel cationic chains were characterized by X‐ray crystallography, NMR spectroscopy and mass spectrometry. Moreover, the formation of the parent complexes [IDipp ⋅ GeH2BH2PH3][OTf] (5) and [IDipp ⋅ GeH3][OTf] (6) were achieved by reaction of 1 with PH3. Accompanying DFT computations give insight into the stability of the formed chains with respect to their decomposition. [ABSTRACT FROM AUTHOR]