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A detailed study of the two-dimensional (2-D) Hofmann-like framework [Fe(furpy)

The use of an angular ligand drives the formation of an irregular Hofmann framework whereby 6-coordinate and rare 5-coordinate FeII species co-exist – the 6-coordinate species show a spin-crossover transition.

The two-dimensional (2-D) framework, [Cu(BTDAT)(MeOH)] {BTDAT = bis-[1,2,5]-thiadiazolo-tetracyanoquinodimethane}, possesses remarkable multi-step redox properties, with electrochemical studies revealing six quasi-stable redox states in the solid state. In situ electron paramagnetic resonance and visible-near infrared spectroelectrochemistry elucidated the mechanism for these multi-step redox processes, as well as the optical and electrochromic behavior of the BTDAT ligand and framework. In studying the structural, spectroscopic, and electronic properties of [Cu(BTDAT)(MeOH)], the as-synthesized framework was found to exist in a mixed-valence state with thermally-activated semiconducting behavior. In addition to pressed pellet conductivity measurements, single-crystal conductivity measurements using a pre-patterned polydimethylsiloxane layer on a silicon substrate provide important insights into the anisotropic conduction pathways. As an avenue to further understand the electronic state of [Cu(BTDAT)(MeOH)], computational band structure calculations predicted delocalized electronic transport in the framework. On the balance of probabilities, we propose that [Cu(BTDAT)(MeOH)] is a Mott insulator (i.e., electron correlations cause a metal-insulator transition). This implies that the conductivity is incoherent. However, we are unable to distinguish between activated transport due to Coulombically bound electron-hole pairs and a hopping mechanism. The combined electrochemical, electronic, and optical properties of [Cu(BTDAT)(MeOH)] shine a new light on the experimental and theoretical challenges for electroactive framework materials, which are implicated as the basis of advanced optoelectronic and electrochromic devices.

Two analogous 2-D Hofmann-type frameworks, which incorporate the novel ligand N-(pyridin-4-yl)benzamide (benpy) [FeII(benpy)2M(CN)4]·2H2O (M = Pd (Pd(benpy)) and Pt (Pt(benpy))) are reported. The benpy ligand was explored to facilitate spin-crossover (SCO) cooperativity via amide group hydrogen bonding. Structural analyses of the 2-D Hofmann frameworks revealed benpy-guest hydrogen bonding and benpy-benpy aromatic contacts. Both analogues exhibited single-step hysteretic spin-crossover (SCO) transitions, with the metal-cyanide linker (M = Pd or Pt) impacting the SCO spin-state transition temperature and hysteresis loop width (Pd(benpy): T½↓↑: 201, 218 K, ∆T: 17 K and Pt(benpy): T½↓↑: 206, 226 K, ∆T: 20 K). The parallel structural and SCO changes over the high-spin to low-spin transition were investigated using variable-temperature, single-crystal, and powder X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry. These studies indicated that the ligand–guest interactions facilitated by the amide group acted to support the cooperative spin-state transitions displayed by these two Hofmann-type frameworks, providing further insight into cooperativity and structure–property relationships.

Foremost, practical applications of spin-crossover (SCO) materials require control of the nature of the spin-state coupling. In existing SCO materials, there is a single, well-defined dimensionality relevant to the switching behavior. A new material, consisting of 1,2,4-triazole-based trimers coordinated into 1D chains by [Au(CN)] and spaced by anions and exchangeable guests, underwent SCO defined by elastic coupling across multiple dimensional hierarchies. Detailed structural, vibrational, and theoretical studies conclusively confirmed that intra-trimer coupling was an order of magnitude greater than the intramolecular coupling, which was an order of magnitude greater than intermolecular coupling. As such, a clear hierarchy on the nature of elastic coupling in SCO materials was ascertained for the first time, which is a necessary step for the technological development of molecular switching materials.

The Cu(II) ions in [(C2H5)3NH]2Cu2(C2O4)3 form a hyperhoneycomb lattice and show no indication of long-range magnetic order down to 60 mK. It has therefore been suggested that [(C2H5)3NH]2Cu2(C2O4)3 is a three dimensional quantum spin liquid. We construct a tight-binding model of [(C2H5)3NH]2Cu2(C2O4)3 from Wannier orbital overlaps. Including interactions within the Jahn–Teller distorted Cu-centered eg Wannier orbitals leads to a highly anisotropic effective Heisenberg model. We show that this anisotropy arrises from interference between different superexchange pathways. This demonstrates that when two (or more) orbitals contribute to the localised spin superexchange can be significantly richer than in the textbook single orbital case. The hyper-honeycomb lattice contains two symmetry distinct sublattices of Cu atoms arranged in coupled chains. We show that one sublattice is strongly dimerized, the other forms isotropic antiferromagnetic chains. Integrating out the strongest (intradimer) exchange interactions leaves extremely weakly coupled Heisenberg chains.

Spin-crossover (SCO) materials display many fascinating behaviors including collective phase transitions and spin-state switching controlled by external stimuli, e.g., light and electrical currents. As single-molecule switches, they have been fêted for numerous practical applications, but these remain largely unrealized-partly because of the difficulty of switching these materials at high temperatures. We introduce a semiempirical microscopic model of SCO materials combining crystal field theory with elastic intermolecular interactions. For realistic parameters, this model reproduces the key experimental results including thermally induced phase transitions, light-induced spin-state trapping (LIESST), and reverse-LIESST. Notably, we reproduce and explain the experimentally observed relationship between the critical temperature of the thermal transition

The Cu(ii) ions in [(C2H5)3NH]2Cu2(C2O4)3 form a hyperhoneycomb lattice and show no indication of long-range magnetic order down to 60 mK. It has therefore been suggested that [(C2H5)3NH]2Cu2(C2O4)3 is a three dimensional quantum spin liquid. We construct a tight-binding model of [(C2H5)3NH]2Cu2(C2O4)3 from Wannier orbital overlaps. Including interactions within the Jahn-Teller distorted Cu-centered eg Wannier orbitals leads to a highly anisotropic effective Heisenberg model. We show that this anisotropy arrises from interference between different superexchange pathways. This demonstrates that when two (or more) orbitals contribute to the localised spin superexchange can be significantly richer than in the textbook single orbital case. The hyper-honeycomb lattice contains two symmetry distinct sublattices of Cu atoms arranged in coupled chains. We show that one sublattice is strongly dimerized, the other forms isotropic antiferromagnetic chains. Integrating out the strongest (intradimer) exchange interactions leaves extremely weakly coupled Heisenberg chains.

Foremost, practical applications of spin-crossover (SCO) materials require control of the nature of the spin-state coupling. In existing SCO materials, there is a single, well-defined dimensionality relevant to the switching behavior. A new material, consisting of 1,2,4-triazole-based trimers coordinated into 1D chains by [Au(CN)

An extended nitro-functionalised 1,2,4-triazole ligand has been used to induce considerable lattice distortion in a 2-D Hofmann framework material via competing supramolecular interactions. Single crystal X-ray diffraction analyses on [Fe3(N-cintrz)6(Pd(CN)4)3]·6H2O (N-cintrz: (E)-3-(2-nitrophenyl)acrylaldehyde) reveal a substantial deviation from a regular Hofmann structure, in particular as the intra- and inter-layer contacts are dominated by hydrogen-bonding interactions rather than the typical π-stacking arrays. Also, the 2-D Hofmann layers show an assortment of ligand conformations and local FeII coordination environments driven by the optimisation of competing supramolecular contacts. Temperature-dependent magnetic susceptibility measurements reveal a two-step spin crossover (SCO) transition. Variable temperature structural analyses show that the two crystallographically distinct FeII centres, which are arranged in stripes (2 : 1 ratio) within each Hofmann layer, undergo a cooperative HS ↔ HS/LS ↔ LS (HS = high spin, LS = low spin) transition without periodic spin-state ordering. The mismatch between crystallographic (2 : 1) and spin-state (1 : 1) periodicity at the HS : LS step provides key insight into the competition (frustration) between elastic interactions and crystallographically driven order.

It has recently been proposed that the dominant non-radiative decay mechanism in blue Ir(III) phosphors at room temperature is due to the low-lying non-radiative metal-centred triplet states. These are populated thermally via an activated transition from the highly radiative metal-to-ligand-charge-transfer states that are initially populated due to intersystem crossing following the radiative or electronic excitation of the phosphor. We apply transition state theory to quantitatively calculate the non-radiative decay rate of a family of Ir(III) complexes containing N-heterocyclic carbene (NHC) ligands. We compare the, computationally inexpensive, one-dimensional theory with the, more accurate, multi-dimensional theory. Both methods find a non-radiative rate with an Arrhenius form (knr = kae−ΔE/kBT). The pre-exponential factors, ka, and activation energies, ΔE, are evaluated via density functional theory (DFT). The multi-dimensional theory shows that there is an order of magnitude variation in ka within this family of materials (between 3 × 1011 s−1 and 3 × 1012 s−1). This is not captured by the one-dimensional theory, which predicts very uniform rate constants in the middle of this range (∼1012 s−1). Nevertheless, the activated process involved, and the linear relationship between ka and knr, mean that ka plays a subtle role in determining knr. Consistent with this we find that both methods capture the trend observed experimentally in the non-radiative rates. Furthermore, the magnitude of the calculated knr is similar in both methods and in good agreement with experimental values [except for one complex with a very shallow activation barrier (

Devices based on deep-blue emitting iridium (III) complexes with N-heterocyclic carbene (NHC) ligands have recently been shown to give excellent performance as phosphorescent organic light-emitting diodes (PHOLEDs). To facilitate the design of even better deep-blue phosphorescent emitters we carried out density functional theory (DFT) calculations of the lowest triplet ($T_1$) potential-energy surfaces (PES) upon lengthening the iridium-ligand (Ir-C) bonds. Relativistic time dependent-DFT (TDDFT) calculations demonstrate that this changes the nature of $T_1$ from a highly-emissive metal-to-ligand charge transfer ($^3$MLCT) state to a metal centered ($^3$MC) state where the radiative decay rate is orders of magnitude slower than that of the $^3$MLCT state. We identify the elongation of an Ir-C bond on the NHC group as the pathway with lowest energy barrier between the $^3$MLCT and $^3$MC states for all complexes studied and show that the barrier height is correlated with the experimentally measured non-radiative decay rate. This suggests that the thermal population of $^3$MC states is the dominant non-radiative decay mechanism at room temperature. We show that the $^3$MLCT $\rightarrow$ $^3$MC transition is reversible, in marked contrast to other deep blue phosphors containing coordinating nitrogen atoms, where the population of $^3$MC states breaks Ir-N bonds. This suggests that, as well as improved efficiency, blue PHOLEDs containing phosphors where the metal is only coordinated by carbon atoms will have improved device lifetimes., 15 pages, 4 figures, 3 tables

We report the synthesis and characterization of a novel thiocarbonyl iso-DPP derivative, namely 1,3,4,6-tetraphenylpyrrolo[3,2-b]pyrrole-2,5(1H,4H)-dithione. Even without solubilising alkyl chains, the small molecule could be processed from organic solvents such as dichloromethane, chloroform or dichlorobenzene, and it was found that the optical properties of neat thin films were strongly dependent on the solvent used. Field effect hole mobilities were of the order 10−4 cm2 V−1 s−1, with mobilities measured in a diode configuration solvent dependent and at least an order of magnitude lower. Importantly, blends of the iso-DPP derivative with PC70BM, a typically used electron acceptor in bulk heterojunction solar cells, were found to possess hole mobilities of up to 10−3 cm2 V−1 s−1 in a diode configuration, which was an order of magnitude larger than the electron mobility. Finally, simple bulk heterojunction solar cells were fabricated with maximum power conversion efficiencies of 2.3%.

The low-energy excitations of iridium(III) complexes, such as fac-Ir(ppy)3, are known to have significant metal-to-ligand charge-transfer character. Hence the degree of exact exchange included in the density functional description of the complex is expected to be important. To investigate this we report both ground state and time-dependent density functional calculations with a range of functionals (with different degrees of exact exchange) and examine the changes in the predictions as we vary the degree of exact exchange within a single functional (while holding the rest of the parameterisation fixed). We find that although the optimal degree of exact exchange (∼20%) gives results in good agreement with experiment for fac-Ir(ppy)3 and the blue emissive fac-Ir(ptz)3, other parameterisations lead to predictions that are both qualitatively and quantitatively inconsistent with experiment. Other differences in the functionals lead to much smaller differences in the predicted properties of the complex. Thus the B3LYP and X3LYP functionals provide the best description of experimental data.

We investigate the role of metal-ligand bond fission in the nonradiative decay of excited states in iridium(III) complexes with applications in blue organic light-emitting diodes (OLEDs). We report density functional theory (DFT) calculations of the potential energy surfaces upon lengthening an iridium-nitrogen (Ir-N) bond. In all cases we find that for bond lengths comparable to those of the ground state the lowest energy state is a triplet with significant metal-to-ligand change transfer character ((3)MLCT). But, as the Ir-N bond is lengthened there is a sudden transition to a regime where the lowest excited state is a triplet with significant metal centered character ((3)MC). Time-dependent DFT relativistic calculations including spin-orbit coupling perturbatively show that the radiative decay rate from the (3)MC state is orders of magnitude slower than that from the (3)MLCT state. The calculated barrier height between the (3)MLCT and (3)MC regimes is clearly correlated with previously measured nonradiative decay rates, suggesting that thermal population of the (3)MC state is the dominant nonradiative decay process at ambient temperature. In particular, fluorination both drives the emission of these complexes to a deeper blue color and lowers the (3)MLCT-(3)MC barrier. If the Ir-N bond is shortened in the (3)MC state another N atom is pushed away from the Ir, resulting in the breaking of this bond, suggesting that once the Ir-N bond breaks the damage to the complex is permanent-this will have important implications for the lifetimes of devices using this type of complex as the active material. The consequences of these results for the design of more efficient blue phosphors for OLED applications are discussed.

The lowest energy triplet state, T1, of organometallic complexes based on iridium(III) is of fundamental interest, as the behavior of molecules in this state determines the suitability of the complex for use in many applications, e.g., organic light-emitting diodes. Previous characterization of T1 in fac-Ir(ppy)3 suggests that the trigonal symmetry of the complex is weakly broken in the excited state. Here we report relativistic time dependent density functional calculations of the zero-field splitting (ZFS) of fac-Ir(ppy)3 in the ground state (S0) and lowest energy triplet (T1) geometries and at intermediate geometries. We show that the energy scale of the geometry relaxation in the T1 state is large compared to the ZFS. Thus, the natural analysis of the ZFS and the radiative decay rates, based on the assumption that the structural distortion is a small perturbation, fails dramatically. In contrast, our calculations of these quantities are in good agreement with experiment.

Ligand substitution is often used for tuning the emission color of phosphorescent iridium(iii) complexes that are used in organic light-emitting diodes. However, in addition to tuning the emission color, the substituents can also affect the radiative and non-radiative decay rates of the excited state and hence the photoluminescence quantum yield. Understanding the substituent effect is therefore important for the design of new iridium(iii) complexes with specific emission properties. Using (time dependent) density functional methods, we investigate the substituent effect of n-propyl groups on the structure, emission color, and emission efficiency of fac-tris(1-methyl-5-phenyl-[1,2,4]triazolyl)iridium(iii) based phosphorescent complexes by comparing the calculated results for structural models with and without the n-propyl substituents. We find that attachment of the n-propyl groups increases the length of three Ir–N bonds, and although the emission color does not change significantly, the radiative and non-radiative rates do, leading to a prediction of enhanced blue phosphorescence emission efficiency. Furthermore, the calculations show that the attachment of the n-propyl groups leads to a larger activation energy to degradation and the formation of dark states.

Melanin, the human skin pigment, is found everywhere in nature. Recently it has gained significant attention for its potential bioelectronic properties. However, there remain significant obstacles in realizing its electronic potential, in particular, the identity of the solid-state free radical in eumelanin, which has been implicated in charge transport. We have therefore undertaken a hydration-controlled continuous-wave electron paramagnetic resonance study on solid-state eumelanin. Herein we show that the EPR signal from solid-state eumelanin arises predominantly from a carbon-centered radical but with an additional semiquinone free radical component. Furthermore, the spin densities of both of these radicals can be manipulated using water and pH. In the case of the semiquinone radical, the comproportionation reaction governs the pH- and hydration-dependent behavior. In contrast, the mechanism underlying the carbon-centered radical's pH- and hydration-dependent behavior is not clear; consequently, we have proposed a new destacking model in which the intermolecular structure of melanin is disordered due to π-π destacking, brought about by the addition of water or increased pH, which increases the proportion of semiquinone radicals via the comproportionation reaction.

The effect of varying the emitter concentration on the structural properties of an archetypal phosphorescent blend consisting of 4,4′-bis(N-carbazolyl)biphenyl and tris(2-phenylpyridyl)iridium(III) has been investigated using non-equilibrium molecular dynamics (MD) simulations that mimic the process of vacuum deposition. By comparison with reflectometry measurements, we show that the simulations provide an accurate model of the average density of such films. The emitter molecules were found not to be evenly distributed throughout film, but rather they can form networks that provide charge and/or energy migration pathways, even at emitter concentrations as low as ≈5 weight percent. At slightly higher concentrations, percolated networks form that span the entire system. While such networks would give improved charge transport, they could also lead to more non-radiative pathways for the emissive state and a resultant loss of efficiency.

We report the electronic properties of a new class of non-fullerene electron acceptor molecules with electron affinities tunable over an approximately 1 eV range. This tunability allows us to vary the thermodynamic driving force for electron transfer (ΔG°) such that it is equal-and-opposite-to the reorganization energy for the ionized states (λ). We utilize this design principle, derived from Marcus–Hush theory, to optimize the rate of charge transfer in blends of these acceptors with poly(3-n-hexylthiophene-2,5-diyl) (P3HT) – a standard organic solar cell donor material. We show that computationally inexpensive calculations can be used to parameterize Marcus–Hush theory so as to correctly predict whether quenching will occur. Arguments based solely on energetics are common in the literature and we show that such theories do not predict the trends observed in our photoluminescence quenching experiments. This is the case whether the energies determined from experiments [cyclic voltammetry (CV) and the optical gap] or calculated from density functional theory for the solid state. We predict essentially barrier-less photoelectron transfer (PET) from P3HT to the acceptor 2-[{7-(9,9-di-n-propyl-9H-fluoren-2-yl)benzo[c] [1] , [2] , [5] thiadiazol-4-yl}methylene]malononitrile (or K12), consistent with the experimental photoluminescence quenching efficiencies found for P3HT:K12 blends. Our results clearly show that energetics alone is not sufficient to predict PET between the acceptor–donor pair, and that kinetics are an important determining factor.

We explore the magnetic properties of isolated a - b planes of trinuclear organometallic crystals, Mo3S7(dmit)3, in which an interplay of strong electronic correlations and spin molecular-orbital coupling (SMOC) occurs. The magnetic properties can be described by a XXZ+1200, S = 1 Heisenberg model on a honeycomb lattice with single-spin anisotropy, D, which depends strongly on SMOC. Based on ab initio estimates of SMOC in Mo3S7(dmit)3 crystals, we predict that the honeycomb layers of Mo3S7(dmit)3 are N´eel ordered. However, in materials with a greater degree of magnetic frustration, N´eel order can give way to a large-D phase, J. M. acknowledges financial support from (MAT2015-66128-R) MINECO/FEDER, UE, and A.R. from the French National Research Agency (Contract ORGANISO, ANR-15-CE09- 0017). Work at the University of Queensland was supported by the Australian Research Council (DP160100060)

Melanins are pigmentary macromolecules found throughout the biosphere that, in the 1970s, were discovered to conduct electricity and display bistable switching. Since then, it has been widely believed that melanins are naturally occurring amorphous organic semiconductors. Here, we report electrical conductivity, muon spin relaxation, and electron paramagnetic resonance measurements of melanin as the environmental humidity is varied. We show that hydration of melanin shifts the comproportionation equilibrium so as to dope electrons and protons into the system. This equilibrium defines the relative proportions of hydroxyquinone, semiquinone, and quinone species in the macromolecule. As such, the mechanism explains why melanin at neutral pH only conducts when “wet” and suggests that both carriers play a role in the conductivity. Understanding that melanin is an electronic-ionic hybrid conductor rather than an amorphous organic semiconductor opens exciting possibilities for bioelectronic applications such as ion-to-electron transduction given its biocompatibility.

Calculating electron-vibration (vibronic) interaction constants is computationally expensive. For molecules containing N nuclei it involves solving the Schrodinger equation for Ο(3N) nuclear configurations in addition to the cost of determining the vibrational modes. We show that quantum vibronic interactions are proportional to the classical atomic forces induced when the total charge of the system is varied. This enables the calculation of vibronic interaction constants from O(1) solutions of the Schrodinger equation. We demonstrate that the O(1) approach produces numerically accurate results by calculating the vibronic interaction constants for several molecules. We investigate the role of molecular vibrations in the Mott transition in κ-(BEDT-TTF)2Cu[N(CN)2]Br.

We present absorption and emission spectra of 5,6-dihydroxyindole-2-carboxylic acid (DHICA), a key melanin monomer, which violate mirror symmetry, and propose that this violation is due to convergent excited-state intramolecular proton-transfer photocycles. Dual features in the absorption spectra arise from excitation into the S1 and S2 states of a catecholate anion form of DHICA. Emission arises from the S1 state of its proton-transfer conjugate following conversion via dual adiabatic and nonadiabatic reaction paths. In support of our postulated mechanism, we offer results from ab initio equation-of-motion coupled cluster (EOM-CCSD) and multistate multireference second-order perturbation theory (MS-MRPT2) calculations. Melanin pigments display an extremely broad, monotonically decreasing absorbance indicative of a dense, coupled manifold of excited states with varying localization character. Our results raise the possibility that intramonomer proton transfer may function as an energy dissipation mechanism from high-lying photoexcited states of the macromolecule.

We give a quantitative analysis of the previously published nuclear magnetic resonance (NMR) experiments in the k-(ET)2X family of organic charge transfer salts by using the phenomenological spin fluctuation model of Moriya, and Millis, Monien and Pines (M-MMP). For temperatures above T_nmr ~ 50 K, the model gives a good quantitative description of the data in the metallic phases of several k-(ET)2X materials. These materials display antiferromagnetic correlation lengths which increase with decreasing temperature and grow to several lattice constants by T_nmr. It is shown that the fact that the dimensionless Korringa ratio is much larger than unity is inconsistent with a broad class of theoretical models (such as dynamical mean-field theory) which neglects spatial correlations and/or vertex corrections. For materials close to the Mott insulating phase the nuclear spin relaxation rate, the Knight shift and the Korringa ratio all decrease significantly with decreasing temperature below T_nmr. This cannot be described by the M-MMP model and the most natural explanation is that a pseudogap, similar to that observed in the underdoped cuprate superconductors, opens up in the density of states below T_nmr. Such a pseudogap has recently been predicted to occur in the dimerised organic charge transfer salts materials by the resonating valence bond (RVB) theory. We propose specific new experiments on organic superconductors to elucidate these issues. For example, measurements to see if high magnetic fields or high pressures can be used to close the pseudogap would be extremely valuable., Comment: 11 pages, 2 figures. Accepted for publication in Phys. Rev. B

We report first principles density functional calculations for hydroquinone (HQ), indolequinone (IQ) and semiquinone (SQ). These molecules are believed to be the basic building blocks of the eumelanins, a class of bio-macromolecules with important biological functions (including photoprotection) and with potential for certain bioengineering applications. We have used the DeltaSCF (difference of self consistent fields) method to study the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), Delta_HL. We show that Delta_HL is similar in IQ and SQ but approximately twice as large in HQ. This may have important implications for our understanding of the observed broad band optical absorption of the eumelanins. The possibility of using this difference in Delta_HL to molecularly engineer the electronic properties of eumelanins is discussed. We calculate the infrared and Raman spectra of the three redox forms from first principles. Each of the molecules have significantly different infrared and Raman signatures, and so these spectra could be used in situ to non-destructively identify the monomeric content of macromolecules. It is hoped that this may be a helpful analytical tool in determining the structure of eumelanin macromolecules and hence in helping to determine the structure-property-function relationships that control the behaviour of the eumelanins., 10 pages, 7 figures

The synthesis of three pyrrolo[3,2-b]pyrrole-1,4-dione (isoDPP) derivatives is described, namely 1,3,4,6-tetraphenylpyrrolo[3,2-b]pyrrole-2,5(1H,4H)-dione 2, 1,4-diphenyl-3,6-di(thiophen-2-yl)pyrrolo[3,2-b]pyrrole-2,5(1H,4H)-dione 3, and 1,4-bis(4-(hexyloxy)phenyl)-3,6-di(thiophen-2-yl)pyrrolo[3,2-b]pyrrole-2,5(1H,4H)-dione 7 in which the molecular structures differ in the aromatic ring (phenyl or thiophene) attached to the nitrogen atom. Thin films of 2, 3, and 7 could be formed by evaporation under vacuum. In the case of 2 and 3 GIWAXS measurements showed that the film structural ordering was similar to that measured in single crystals. In contrast GIWAXS showed that 7 had features associated with liquid crystalline materials. Time dependent density functional theory (TDDFT) calculations predicted that the transition between the lowest energy singlet excitation (S1) and the ground state (S0) would be optically forbidden due to the centrosymmetric geometries of compounds. Photophysical measurements showed that the compounds were weakly luminescent, with low radiative rates in solution of order 106 s−1, which are consistent with the TDDFT predictions. Furthermore, photoinduced absorption (PIA) spectroscopy showed that there is a long-lived low energy state, which has been assigned as a triplet and provides a further non-radiative decay pathway for the excited state.