Search

Sapphyrin is a pentapyrrolic expanded porphyrin with a 22π aromatic character. Herein, we report the synthesis of a 20π antiaromatic sapphyrin isomer 1 by oxidative cyclization of a pentapyrrane precursor P5 with a terminal β‐linked pyrrole. The resulting isomer 1, containing a mis‐linked bipyrrole unit in the skeleton, exhibits a reactivity for further oxidation due to the distinct antiaromatic electronic structure, affording a fused macrocycle 2, possessing a spiro‐carbon‐containing [5.6.5.6]‐tetracyclic structure. Subsequent treatment with an acid afforded a weakly aromatic pyrrolone‐appended N‐confused corrole 3, and thermal fusion gave a [5.6.5.7]‐tetracyclic‐ring‐embedded 14π aromatic triphyrin(2.1.1) analog 4. The cyclization at the mis‐linked pyrrole moiety of P5 played a crucial role in synthesizing the antiaromatic porphyrinoid susceptible to facile transformation to novel porphyrinoids with variable aromaticity. [ABSTRACT FROM AUTHOR]

In this work, organic concerted companion (CC) dyes CCOD‐1 and CCOD‐2 were constructed by covalently linking two organic dye units with complementary absorption spectra. Both CC dyes exhibited intense absorption from 300 to 650 nm with the band edges extended to 700 nm. These CC dyes were used to fabricate dye‐sensitized solar cells (DSSCs), and the photovoltaic performance was investigated using different light sources. CCOD‐2 possessed bulkier outer shelter than CCOD‐1 owing to the longer carbon chains (C12) at the donor moiety, and thus it had stronger anti‐aggregation and anti‐charge‐recombination ability. Under simulated sunlight (AM1.5G), CCOD‐2 exhibited enhanced photovoltaic behavior with an open‐circuit voltage (VOC) of 759 mV, short‐circuit current density (JSC) of 19.23 mA ⋅ cm−2, and power conversion efficiency (PCE) of 10.4 %, respectively. Notably, under the illumination of the indoor T5 fluorescent lamp (2500 lux), CCOD‐2 afforded an enhanced PCE of 28.0 % with remarkable VOC and JSC of 692 mV and 0.424 mA cm−2, respectively. Notably, the PCE achieved for CCOD‐2 outperformed those of the reference sensitizer N719 and our previously reported CC dyes XW61 and XW70‐C8 under the same indoor lamp conditions. In summary, the novel organic CC dyes developed in this work were demonstrated to be promising for fabricating DSSCs to efficiently harvest the energy of indoor lamps. [ABSTRACT FROM AUTHOR]

In this work, a novel compound 2‐(3,5,6‐trichloro‐1,4‐benzoquinon‐2‐yl)‐neo‐fused hexaphyrin has been prepared from tetrachloroquinone and neo‐fused hexaphyrin through a substitution reaction. The chemical structure of the compound has been characterized by nuclear magnetic resonance (NMR), high‐resolution mass spectrum, UV–Vis spectrum, and X‐ray diffraction. The crystal structure reveals that the quinonyl unit is almost coplanar with the adjacent N‐confused pyrrole unit. Because of the cooperative effect of extended conjugation and the intramolecular charge transfer effect related to the strong electron‐withdrawing character of the quinonyl unit, the absorption of 2 is dramatically extended to ca. 1280 nm. [ABSTRACT FROM AUTHOR]

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face‐to‐face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials. [ABSTRACT FROM AUTHOR]

Oxidation of a thiophene‐hexapyrrane hybrid S‐P6 afforded a stable conjugated open‐chain thiaheptapyrrolic helix 1 with the terminal thiophene and confused pyrrole units lying at a long distance that is adverse for further cyclization. Chelation of 1 with copper(II) ion afforded 1‐Cu, which exhibits more distant terminal units. Interestingly, further oxidation of 1 triggered an intramolecular C−N fusion reaction to afford a unique 5,5,5‐tricyclic fused linear thiaheptapyrrin 2, with the two terminals positioned in proximity, which favors the oxidative ring‐closure reaction to give a unique 5,5,5‐tricyclic fused thiaheptaphyrin (1.1.1.1.1.1.0) 3 under air. The inner‐fusion strategy for positioning the reactive sites in proximity to promote oxidative cyclization offers a new approach for constructing large porphyrinoids through conjugated oligopyrrins without the assistance of metal ions. [ABSTRACT FROM AUTHOR]

An N‐confused phlorin isomer bearing a dipyrrin moiety at the α‐position of the confused pyrrole ring (1) was synthesized. PdII and BIII coordination at the peripheral prodigiosin‐like moiety of 1 afforded the corresponding complexes 2 and 3. Reflux of 2 in triethylamine (TEA) converted the meso‐phenyl into the PdII‐coordinating phenoxy group to afford 4. Under the same reaction conditions, TEA was linked to the α‐position of the dipyrrin unit in 3 as an N,N‐diethylaminovinyl group to afford 5. Furthermore, peripheral coordination of BIII in 3 and 5 improved the planarity of the phlorin macrocycle and thus facilitated the coordination of AgIII at the inner cavity to afford 3‐Ag and 5‐Ag, respectively. These results provide an effective approach for developing unique porphyrinoids through peripheral coordination. [ABSTRACT FROM AUTHOR]

A series of new porphyrin dyes (XW42–XW44) containing oligo(ethylene glycol) units have been designed and synthesized. Two triethylene glycol units were introduced into the phenothiazine moiety of XW42, whereas diethylene glycol (DEG) and ethylene glycol chains were introduced to afford XW43 and XW44, respectively. Interestingly, the efficiencies of the DSSCs were clearly dependent on the chain lengths. Among the three dyes, XW42 and XW43 exhibited relatively high open‐circuit voltages of 751 and 750 mV, respectively, and XW43 exhibited the highest efficiency of 10.32 % owing to the presence of the DEG chains with suitable lengths and excellent ability to trap Li+. Furthermore, through a combined coadsorption and cosensitization approach, the efficiencies were dramatically enhanced. As a result, a highest efficiency of 12.10 % was obtained for the XW43+chenodeoxycholic acid+PT‐C6 (a metal‐free organic dye) system, which ranks among the highest efficiencies of cells based on the traditional iodine electrolyte. [ABSTRACT FROM AUTHOR]

A hybrid thia‐norhexaphyrin comprising a directly linked N‐confused pyrrole and thiophene unit (1) revealed unique macrocycle transformations to afford multiply inner‐annulated aromatic macrocycles. Oxidation with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone triggered a cleavage of the C−S bond of the thiophene unit, accompanied with skeletal rearrangement to afford unique π‐conjugated products: a thiopyrrolo‐pentaphyrin embedded with a pyrrolo[1,2]isothiazole (2), a sulfur‐free pentaphyrin incorporating an indolizine moiety (3), and a thiopyranyltriphyrinoid containing a 2H‐thiopyran unit (4). Furthermore, 2 underwent desulfurization reactions to afford a fused pentaphyrin containing a pyrrolizine moiety (5) under mild conditions. Using expanded porphyrin scaffolds, oxidative thiophene cleavage and desulfurization of the hitherto unknown N‐confused core‐modified macrocycles would be a practical approach for developing unique polypyrrolic aromatic macrocycles. Oxidation of a nonaromatic thia‐modified norhexaphyrin with directly linked N‐confused pyrrole and thiophene rings triggered cleavage of a C−S bond to afford three multiply annulated polypyrrolic aromatic macrocycles with global or local aromaticity. This approach is a path to porphyrinoids with tunable structures and aromaticity based on thiophene cleavage and desulfurization. [ABSTRACT FROM AUTHOR]

Three kinds of fused porphyrinoids, L2- L4, possessing different types of corrole-based frameworks were synthesized from a pyrrole-substituted corrole isomer (norrole L1). Oxidation of L1 afforded a unique N-Cmeso-fused pyrrolyl isonorrole L2, involving the fusion of an auxiliary pyrrolic NH moiety with a meso-sp3-hybridized carbon atom. Subsequently, L2 underwent macrocycle transformations to give singly and doubly N-CAr-fused N-confused corroles, L3 and L4, respectively. L3 and L4 contain fused [5.7.6.5]-tetra- and [5.6.7.7.6.5]-hexacyclic structures, respectively, prepared through lateral annulation. These skeletal transformation reactions from norrole to its isomer isonorrole and finally to N-confused corrole indicate that multiply fused porphyrinoids could be readily synthesized from pyrrole-appended confused porphyrinoids. [ABSTRACT FROM AUTHOR]

The rational design of high-performance fluorescent materials for cancer targeting in vivo is still challenging. A unique molecular design strategy is presented that involves tailoring aggregation-induced emission (AIE)-active organic molecules to realize preferable far-red and NIR fluorescence, well-controlled morphology (from rod-like to spherical), and also tumor-targeted bioimaging. The shape-tailored organic quinoline-malononitrile (QM) nanoprobes are biocompatible and highly desirable for cell-tracking applications. Impressively, the spherical shape of QM-5 nanoaggregates exhibits excellent tumor-targeted bioimaging performance after intravenously injection into mice, but not the rod-like aggregates of QM-2. [ABSTRACT FROM AUTHOR]

The first neo-confused hexaphyrin(1.1.1.1.1.0) was synthesized by oxidative ring closure of a hexapyrrane bearing two terminal 'confused' pyrroles. The new compound displays a folded conformation with a short interpyrrolic C⋅⋅⋅N distance of 3.102 Å, and thus it readily underwent ring fusion to afford a neo-fused hexaphyrin with an unprecedented 5,5,5,7-tetracyclic ring structure. Furthermore, coordination of CuII triggered a ring opening/contracting reaction to afford a CuII complex of an N-linked pentaphyrin derivative. The roles of reactive NC bonds in the porphyrinoid macrocycles were demonstrated. [ABSTRACT FROM AUTHOR]

Porphyrin dyes containing the carbazole electron donor have been designed and optimized by wrapping the porphyrin framework, introducing an additional ethynylene bridge to extend the wavelength range of light absorption, and further suppression of the dye aggregation by introducing additional alkoxy chains. Application of a cosensitization approach results in improved current density ( Jsc) and open-circuit voltage ( Voc) values, thus achieving the highest cell efficiency of 10.45 %. This work provides an effective combined strategy of molecular design and cosensitization for developing efficient dye-sensitized solar cells (DSSCs). In addition, carbazole has been demonstrated to be a promising donor for porphyrin sensitizers. [ABSTRACT FROM AUTHOR]

Compared with most of the reported logic devices based on the supramolecular approach, systems based on individual molecules can avoid challenging construction requirements. Herein, a novel dioxoporphyrin DPH22 was synthesized and two of its tautomers were characterized by single-crystal X-ray diffraction studies. Compound DPH22 exhibits multichannel controllable stepwise tautomerization, protonation, and deprotonation processes through interactions with H+ and F− ions. By using the addition of H+ and F− ions as inputs and UV/Vis absorption values at λ=412, 510, 562, and 603 nm as outputs, the controlled tautomerism of DPH22 has been successfully used for the construction of an integrated molecular level half-subtractor and comparator. In addition, this acid/base-switched tautomerism is reversible, thus endowing the system with ease of reset and recycling; consequently, there is no need to modulate complicated intermolecular interactions and electron-/charge-transfer processes. [ABSTRACT FROM AUTHOR]

Endowing both solvent independency and excellent thermal bistability, the benzobis(thiadiazole)-bridged diarylethene system provides an efficient approach to realize extremely high photocyclization quantum yields ( Φo-c, up to 90.6 %) by both separating completely pure anti-parallel conformer and suppressing intramolecular charge transfer (ICT). [ABSTRACT FROM AUTHOR]

Using one ray of light to encode another ray of light is highly desirable because information in optical format can be directly transferred from one beam to another without converting back to the electronic format. One key medium to accomplish such an amazing task is photoswitchable molecules. Using bis(dithiazole)ethene that can be photoswitched between its ring‐open and ring‐closed states quantitatively with excellent fatigue resistance and high thermal stability, it is shown that quantitative photoreversibility allowed the photoswitching light to control other light travelling through the photoswitchable medium, a phenomenon of transferring information encoded in one light ray to others, thus imparting photo‐optical modulation on the orthogonal light beam. [ABSTRACT FROM AUTHOR]

Complexes of new Schiff base ligands generated in situ from the reaction of 1-aminoglycerol, aldehydes, and metal ions are reported. [Cu4(HL1)4] ( 1) and [Ni4O(HL1)3(H2O)3)] ⋅6 H2O ⋅DMF ⋅DMSO ( 2) have M4O4 cubane cores, with the L/M molar ratios of 4:4 and 3:4, respectively. [MnIII3MnIINaOCl4(HL1)3] ⋅3 MeCN ( 3) has a unique pentanuclear trigonal propeller-shaped MnIII3MnIINa core structure, and the coordination assemblies are linked by hydrogen bonds to afford a 3D channel structure. [Cu2(HL2)2] ( 4) has a bis(μ2-alkoxo)-bridged Cu2O2 core, with the binuclear species linked by hydrogen bonds to afford a 1D double-chain. [Ni7(OH)2(OCH3)4(H2L3)2(MeOH)2(H2O)2]- (ClO4)2 ⋅10 H2O ( 5) has a heptanuclear structure containing heptadentate di-Schiff base ligands, with the nickel(II) ions bridged by phenoxo, alkoxo, hydroxo, and methoxo groups to afford a very rare face-sharing hexadruple defective cubane core with a Ni@Ni6 arrangement. The lattice water molecules are linked by hydrogen bonds to form helical chains, which are further hydrogen-bonded to the coordination moieties to afford a 2D network. Variable temperature magnetic susceptibility measurements and nonlinear data-fitting revealed that the '2+4' type of cubane complex 1 shows medium intradimeric ferromagnetic interactions and weak interdimeric ferromagnetic interactions. For complexes 2 and 5, coexistent ferro- and antiferromagnetic couplings afford a non-zero spin ground state. However, compound 3 shows antiferromagnetic interactions between MnIII and MnII, and ferromagnetic interactions between the MnIII centers, resulting in a global antiferromagnetic behavior. In conclusion, the reaction of 1-aminoglycerol with aldehydes and metal salts afforded polynuclear complexes with a rich structural diversity and remarkable magnetic behavior. [ABSTRACT FROM AUTHOR]

Three photochromic compounds-2-butyl-5,6-bis[5-(4-methoxyphenyl)-2-methylthiophen-3-yl]-1 H-benzo[ de]isoquinoline-1,3(2 H)-dione (BTE-NA), 4,5-bis[5-(4-methoxyphenyl)-2-methylthiophen-3-yl]benzo[ c][1,2,5]thiadiazole (BTA), and BTTA, which contain naphthalimide, benzothiadiazole, and benzobisthiadiazole as six-membered ethene bridges with different aromaticities-were systematically studied in solution, sol-gel, and single-crystal states. They exhibit typical photochromic performance with considerably high cyclization quantum yields. BTE-NA, BTA, and BTTA form a typical donor-π-acceptor ( D-π-A) system with significant intramolecular charge transfer (ICT) between HOMO and LUMO upon excitation, thus realizing the fluorescence modulation by both photochromism and solvatochromism. The three ethene bridges with different degrees of aromaticity can provide a systematic comparison of the thermal stability evolution for their corresponding closed forms (c-BTE-NA, c-BTA, and c-BTTA). c-BTE-NA shows first-order decay in various solvents from cyclohexane to acetonitrile. c-BTA only shows first-order decay in polar solvents such as chloroform, whereas it is stable in nonpolar solvents like toluene. In contrast, the less aromatic property of BTTA gives rise to its unprecedented thermal stability in various solvents even at elevated temperatures in toluene (328 K). Moreover, the small energy barrier between the parallel and antiparallel conformers allows the full conversion from BTTA to c-BTTA. In well-ordered crystal states, all three compounds adopt a parallel conformation. Interestingly, BTTA forms a twin crystal of asymmetric nature with interactions between the electron-rich oxygen atom of the methoxy group and the carbon atom of the electron-deficient benzobisthiadiazole moiety. This work contributes to the understanding of aromaticity-controlled thermal stability of photochromic systems based on a six-membered ring as an ethene bridge, and a broadening of the novel building blocks for photochromic bisthienylethene systems. [ABSTRACT FROM AUTHOR]

Anticoagulation factor I (ACF I) isolated from the venom of Agkistrodon acutus is an activated coagulation factor X-binding protein in a Ca2+-dependent fashion with marked anticoagulant activity. The equilibrium unfolding/refolding of apo-ACF I, holo-ACF I, and Tb3+-reconstituted ACF I in guanidine hydrochloride (GdnHCl) solutions was studied by following the fluorescence and circular dichroism. Metal ions were found to increase the structural stability of ACF I against GdnHCl and thermal denaturation and, furthermore, influence its unfolding/refolding behavior. The GdnHCl-induced unfolding/refolding of both apo-ACF I and Tb3+-ACF I is a two-state process with no detectable intermediate state(s), whereas the GdnHCl-induced unfolding/refolding of holo-ACF I in the presence of 1 mM Ca2+ follows a three-step transition, with intermediate state a (Ia) and intermediate state b (Ib). Ca2+ ions play an important role in the stabilization of the Ia and Ib states. The decalcification of holo-ACF I shifts the ending zone of unfolding/refolding curve toward lower GdnHCl concentration, whereas the reconstitution of apo-ACF I with Tb3+ ions shifts the initial zone of denaturation curve toward higher GdnHCl concentration. Therefore, it is possible to find a denaturant concentration (2.0 M GdnHCl) at which refolding from the fully denatured state of apo-ACF I to the Ib state of holo-ACF I or to the native state of Tb3+-ACF I can be initiated merely by adding the 1 mM Ca2+ ions or 10 μM Tb3+ ions to the unfolded state of apo-ACF I, respectively, without changing the concentration of the denaturant. Using Tb3+ as a fluorescence probe of Ca2+, the kinetic results of metal ions-induced refolding provide evidence that the compact Tb3+-binding region forms first, and subsequently, the protein undergoes further conformational rearrangements to form the native structure. [ABSTRACT FROM AUTHOR]