Morphology, dynamic disorder, and charge transport in an indoloindole-based hole-transporting material from a multi-level theoretical approach.

The exponential effort in the design of hole-transporting materials (HTMs) during the last decade has been motivated by their key role as p-type semiconductors for (opto)electronics. Although structure-property relationships have been successfully rationalized to decipher optimal site substitutions, aliphatic chain lengths or efficient aromatic cores for enhanced charge conduction, the impact of molecular shape, material morphology and dynamic disorder has been generally overlooked. In this work, we characterize by means of a multi-level theoretical approach the charge transport properties of a novel planar small-molecule HTM based on the indoloindole aromatic core (IDIDF), and compare it with spherical spiro-OMeTAD. Hybrid DFT calculations predict moderate band dispersions in IDIDF associated to the main transport direction characterized by π-π stacked molecules, both between the indoloindole cores and the thiophene groups. Strongly coupled dimers show relevant non-covalent interactions (NCI), indicating that NCI surfaces are a necessary but not exclusive requirement for large electronic couplings. We evidence remarkable differences in the site energy standard deviation and electronic coupling distributions between the conduction paths of IDIDF and spiro-OMeTAD. Despite the spherical vs. planar shape, theoretical calculations predict in the static crystal strong direction-dependent charge transport in the two HTMs, with ca. one-order-of-magnitude higher mobility (µ) for IDIDF. The dynamical disorder promoted by finite temperature effects in the crystal leads to a reduction in the hole transport properties in both HTMs, with maximum µ values of 2.42 and 4.2 × 10-2 cm2 V-1 s-1 for IDIDF and spiro-OMeTAD, respectively, as well as a significant increase in the transport anisotropy in the latter. Finally, the impact of the material amorphousness in the hole mobility is analysed by modelling a fully random distribution of HTM molecules. An average (lower-bound) mobility of 1.1 × 10-3 and 4.9 × 10-5 cm2 V-1 s-1 is predicted for planar IDIDF and spherical spiro-OMeTAD, respectively, in good accord with the experimental data registered in thin-film devices. Our results demonstrate the strong influence of molecular shape, dynamic structural fluctuations and crystal morphology on the charge transport, and pose indoloindole-based HTMs as promising materials for organic electronics and photovoltaics.

Theoretical description of photoinduced electron transfer in donor-acceptor supramolecular complexes based on carbon buckybowls.

Herein, we explore, from a theoretical perspective, the nonradiative photoinduced processes (charge separation and energy transfer) within a family of donor-acceptor supramolecular complexes based on the electron-donor truxene-tetrathiafulvalene (truxTTF) derivative and a series of curved fullerene fragments (buckybowls) of different shapes and sizes (C30H12, C32H12, and C38H14) as electron acceptors that successfully combine with truxTTF via non-covalent interactions. The resulting supramolecular complexes (truxTTF·C30H12, truxTTF·C32H12, and truxTTF·C38H14) undergo charge-separation processes upon photoexcitation through charge-transfer states involving the donor and acceptor units. Despite the not so different size of the buckybowls, they present noticeable differences in the charge-separation efficiency owing to a complex decay post-photoexcitation mechanism involving several low-lying excited states of different natures (local and charge-transfer excitations), all closely spaced in energy. In this intricate scenario, we have adopted a theoretical approach combining electronic structure calculations at (time-dependent) density functional theory, a multistate multifragment diabatization method, the Marcus-Levitch-Jortner semiclassical rate expression, and a kinetic model to estimate the charge separation rate constants of the supramolecular heterodimers. Our outcomes highlight that the efficiency of the photoinduced charge-separation process increases with the extension of the buckybowl backbone. The supramolecular heterodimer with the largest buckybowl (truxTTF·C38H14) displays multiple and efficient electron-transfer pathways, providing a global photoinduced charge separation in the ultrafast time scale in line with the experimental findings. The study reported indicates that modifications in the shape and size of buckybowl systems can give rise to attractive novel acceptors for potential photovoltaic applications.

Implementing Mesoporosity in Zeolitic Imidazolate Frameworks through Clip-Off Chemistry in Heterometallic Iron-Zinc ZIF-8.

Bond breaking has emerged as a new tool to postsynthetically modify the pore structure in metal-organic frameworks since it allows us to obtain pore environments in structures that are inaccessible by other techniques. Here, we extend the concept of clip-off chemistry to archetypical ZIF-8, taking advantage of the different stabilities of the bonds between imidazolate and Zn and Fe metal atoms in heterometallic Fe-Zn-ZIF-8. We demonstrate that Fe centers can be removed selectively without affecting the backbone of the structure that is supported by the Zn atoms. This allows us to create mesopores within the highly stable ZIF-8 structure. The strategy presented, combined with control of the amount of iron centers incorporated into the structure, permits porosity engineering of ZIF materials and opens a new avenue for designing novel hierarchical porous frameworks.

Perylene-Based Coordination Polymers: Synthesis, Fluorescent J-Aggregates, and Electrochemical Properties.

The incorporation of electroactive organic building blocks into coordination polymers (CPs) and metal-organic frameworks (MOFs) offers a promising approach for adding electronic functionalities such as redox activity, electrical conductivity, and luminescence to these materials. The incorporation of perylene moieties into CPs is, in particular, of great interest due to its potential to introduce both luminescence and redox properties. Herein, we present an innovative synthesis method for producing a family of highly crystalline and stable coordination polymers based on perylene-3,4,9,10-tetracarboxylate (PTC) and various transition metals (TMs = Co, Ni, and Zn) with an isostructural framework. The crystal structure of the PTC-TM CPs, obtained through powder X-ray diffraction and Rietveld refinement, provides valuable insights into the composition and organization of the building blocks within the CP. The perylene moieties are arranged in a herringbone pattern, with short distances between adjacent ligands, which contributes to the dense and highly organized framework of the material. The photophysical properties of PTC-Zn were thoroughly studied, revealing the presence of J-aggregation-based and monomer-like emission bands. These bands were experimentally identified, and their behavior was further understood through the use of quantum-chemical calculations. Solid-state cyclic voltammetry experiments on PTC-TMs showed that the perylene redox properties are maintained within the CP framework. This study presents a simple and effective approach for synthesizing highly stable and crystalline perylene-based CPs with tunable optical and electrochemical properties in the solid state.

Semiconductor Porous Hydrogen-Bonded Organic Frameworks Based on Tetrathiafulvalene Derivatives.

Herein, we report on the use of tetrathiavulvalene-tetrabenzoic acid, H4TTFTB, to engender semiconductivity in porous hydrogen-bonded organic frameworks (HOFs). By tuning the synthetic conditions, three different polymorphs have been obtained, denoted MUV-20a, MUV-20b, and MUV-21, all of them presenting open structures (22, 15, and 27%, respectively) and suitable TTF stacking for efficient orbital overlap. Whereas MUV-21 collapses during the activation process, MUV-20a and MUV-20b offer high stability evacuation, with a CO2 sorption capacity of 1.91 and 1.71 mmol g-1, respectively, at 10 °C and 6 bar. Interestingly, both MUV-20a and MUV-20b present a zwitterionic character with a positively charged TTF core and a negatively charged carboxylate group. First-principles calculations predict the emergence of remarkable charge transport by means of a through-space hopping mechanism fostered by an efficient TTF π-π stacking and the spontaneous formation of persistent charge carriers in the form of radical TTF•+ units. Transport measurements confirm the efficient charge transport in zwitterionic MUV-20a and MUV-20b with no need for postsynthetic treatment (e.g., electrochemical oxidation or doping), demonstrating the semiconductor nature of these HOFs with record experimental conductivities of 6.07 × 10-7 (MUV-20a) and 1.35 × 10-6 S cm-1 (MUV-20b).

Distance Matters: Biasing Mechanism, Transfer of Asymmetry, and Stereomutation in N-Annulated Perylene Bisimide Supramolecular Polymers.

The synthesis of two series of N-annulated perylene bisimides (PBIs), compounds 1 and 2, is reported, and their self-assembling features are thoroughly investigated by a complete set of spectroscopic measurements and theoretical calculations. The study corroborates the enormous influence that the distance between the PBI core and the peripheral groups exerts on the chiroptical properties and the supramolecular polymerization mechanism. Compounds 1, with the peripheral groups separated from the central PBI core by two methylenes and an ester group, form J-type supramolecular polymers in a cooperative manner but exhibit negligible chiroptical properties. The lack of clear helicity, due to the staircase arrangement of the self-assembling units in the aggregate, justifies these features. In contrast, attaching the peripheral groups directly to the N-annulated PBI core drastically changes the self-assembling properties of compounds 2, which form H-type aggregates following an isodesmic mechanism. These H-type aggregates show a strong aggregation-caused quenching (ACQ) effect that leads to nonemissive aggregates. Chiral (S)-2 and (R)-2 experience an efficient transfer of asymmetry to afford P- and M-type aggregates, respectively, although no amplification of asymmetry is achieved in majority rules or "sergeants-and-soldiers" experiments. A solvent-controlled stereomutation is observed for chiral (S)-2 and (R)-2, which form helical supramolecular polymers of different handedness depending on the solvent (methylcyclohexane or toluene). The stereomutation is accounted for by considering the two possible conformations of the terminal phenyl groups, eclipsed or staggered, which lead to linear or helical self-assemblies, respectively, with different relative stabilities depending on the solvent.

Selective CO2 Sorption Using Compartmentalized Coordination Polymers with Discrete Voids*.

Carbon capture and storage with porous materials is one of the most promising technologies to minimize CO2 release into the atmosphere. Here, we report a family of compartmentalized coordination polymers (CCPs) capable of capturing gas molecules in a selective manner based on two novel tetrazole-based ligands. Crystal structures have been modelled theoretically under the Density Functional Theory (DFT) revealing the presence of discrete voids of 380 Å3 . Single gas adsorption isotherms of N2 , CH4 and CO2 have been measured, obtaining a loading capacity of 0.6, 1.7 and 2.2 molecules/void at 10 bar and at 298 K for the best performing material. Moreover, they present excellent selectivity and regenerability for CO2 in mixtures with CH4 and N2 in comparison with other reported materials, as evidenced by dynamic breakthrough gas experiments. These frameworks are therefore great candidates for separation of gas mixtures in the chemical engineering industry.

Charge-Separation and Charge-Recombination Rate Constants in a Donor-Acceptor Buckybowl-Based Supramolecular Complex: Multistate and Solvent Effects.

The kinetics of the nonradiative photoinduced processes (charge-separation and charge-recombination) experimented in solution by a supramolecular complex formed by an electron-donating bowl-shaped truxene-tetrathiafulvalene (truxTTF) derivative and an electron-accepting fullerene fragment (hemifullerene, C30H12) has been theoretically investigated. The truxTTF·C30H12 heterodimer shows a complex decay mechanism after photoexcitation with the participation of several low-lying excited states of different nature (local and charge-transfer excitations) all close in energy. In this scenario, the absolute rate constants for all of the plausible charge-separation (CS) and charge-recombination (CR) channels have been successfully estimated using the Marcus-Levich-Jortner (MLJ) rate expression, electronic structure calculations, and a multistate diabatization method. The outcomes suggest that for a reasonable estimate of the CS and CR rate constants, it is necessary to include the following: (i) optimally tuned long-range (LC) corrected density functionals, to predict a correct energy ordering of the low-lying excited states; (ii) multistate effects, to account for the electronic couplings; and (iii) environmental solvent effects, to provide a proper stabilization of the charge-transfer excited states and accurate external reorganization energies. The predicted rate constants have been incorporated in a simple but insightful kinetic model that allows estimating global CS and CR rate constants in line with the most generalized three-state model used for the CS and CR processes. The values computed for the global CS and CR rates of the donor-acceptor truxTTF·C30H12 supramolecular complex are found to be in good agreement with the experimental values.

Dual-Mode Chiral Self-Assembly of Cone-Shaped Subphthalocyanine Aromatics.

Columnar polymers and liquid crystals obtained from π-conjugated cone-shaped molecules are receiving increasing interest due to the possibility of obtaining unconventional polar organizations that show anisotropic charge transport and unique chiroptical properties. However, and in contrast to the more common planar discotics, the self-assembly of conic or pyramidic molecules in solution remains largely unexplored. Here, we show how a molecular geometry change, from flat to conic, can generate supramolecular landscapes where different self-assembled species, each of them being under thermodynamic equilibrium with the monomer, exist exclusively within distinct regimes. In particular, depending on the solvent nature-aromatic or aliphatic-cone-shaped C3-symmetric subphthalocyanine 1 can undergo self-assembly either as a tail-to-tail dimer, showing monomer-dimer sigmoidal transitions, or as a head-to-tail noncentrosymmetric columnar polymer, exhibiting a nucleation-elongation polymerization mechanism. Moreover, the experimental and theoretical comparison between racemic and enantiopure samples revealed that the two enantiomers (1M and 1P) tend to narcissistically self-sort in the dimer regime, each enantiomer showing a strong preference to associate with itself, but socially self-sort in the polymer regime, favoring an alternate stacking order along the columns.

Arylazopyrazoles for Long-Term Thermal Energy Storage and Optically Triggered Heat Release below 0 °C.

Arylazopyrazole derivatives based on four core structures (4pzMe, 3pzH, 4pzH, and 4pzH-F2) and functionalized with a dodecanoate group were demonstrated to store thermal energy in their metastable Z isomer liquid phase and release the energy by optically triggered crystallization at -30 °C for the first time. Three heat storage-release schemes were discovered involving different activation methods (optical, thermal, or combined) for generating liquid-state Z isomers capable of storing thermal energy. Visible light irradiation induced the selective crystallization of the liquid phase via Z-to-E isomerization, and the latent heat stored in the liquid Z isomers was preserved for longer than 2 weeks unless optically triggered. Up to 92 kJ/mol of thermal energy was stored in the compounds, demonstrating remarkable thermal stability of Z isomers at high temperatures and liquid-phase stability at temperatures below 0 °C.

Mono- and Tripodal Porphyrins: Investigation on the Influence of the Number of Pyrene Anchors in Carbon Nanotube and Graphene Hybrids.

A series of molecular precursors, containing one (1 and 3) or three (2 and 4) pyrene anchors, covalently linked to porphyrins (free base or Zn), were prepared and characterized. All of them enable their π-π stacking onto low-dimensional nanocarbons including single-walled carbon nanotubes (SWCNTs) and nanographene (NG), their individualization, and their characterization. Microscopic (TEM, AFM) and spectroscopic (steady-state UV-vis and fluorescence, spectroelectrochemistry, and transient absorption measurements) techniques were at the forefront of the characterizations and were complemented by Raman spectroscopy and theoretical calculations. Of great importance is the Raman analysis, which corroborated n-doping of the nanocarbons due to the interactions with 1-4 when probed in the solid state. In solution, the situation is, however, quite different. Efficient charge separation was only observed for the graphene-based system NG/3.

Impact of Molecular Size and Shape on the Supramolecular Co-Assembly of Chiral Tricarboxamides: A Comparative Study.

A comparative investigation of the chiral amplification features of a series of three families of C3 -symmetric tricarboxamides, 1,3,5-triphenylbenzenetricarboxamides (TPBAs), benzenetricarboxamides (BTAs) and oligo(phenylene ethynylene) tricarboxamides (OPE-TAs), is here reported. As previously observed for BTAs and OPE-TAs, a similar dichroic response is obtained for TPBAs decorated with one, two or three chiral side chains bearing stereogenic centers, thus confirming the efficient transfer of point chirality to the supramolecular helical aggregates. Unlike BTAs and OPE-TAs, the chiral amplification ability of TPBAs in majority rules experiments shows a negligible dependence on the number of chiral centers per monomeric unit, and stands the largest among the series of tricarboxamides. Detailed experimental and theoretical studies demonstrate that the rotation angle between the TPBA units in the helical stack is intermediate to that observed for BTAs and OPE-TAs. This feature strongly conditions the steric interactions between vicinal molecules in the stack and the final chiral amplification outcome. Furthermore, theoretical calculations show that achiral side chains favor the interdigitation of the helical aggregates and thereby the formation of bundle superstructures.

Azatruxene-Based, Dumbbell-Shaped, Donor-π-Bridge-Donor Hole-Transporting Materials for Perovskite Solar Cells.

Three novel donor-π-bridge-donor (D-π-D) hole-transporting materials (HTMs) featuring triazatruxene electron-donating units bridged by different 3,4-ethylenedioxythiophene (EDOT) π-conjugated linkers have been synthesized, characterized, and implemented in mesoporous perovskite solar cells (PSCs). The optoelectronic properties of the new dumbbell-shaped derivatives (DTTXs) are highly influenced by the chemical structure of the EDOT-based linker. Red-shifted absorption and emission and a stronger donor ability were observed in passing from DTTX-1 to DTTX-2 due to the extended π-conjugation. DTTX-3 featured an intramolecular charge transfer between the external triazatruxene units and the azomethine-EDOT central scaffold, resulting in a more pronounced redshift. The three new derivatives have been tested in combination with the state-of-the-art triple-cation perovskite [(FAPbI3 )0.87 (MAPbBr3 )0.13 ]0.92 [CsPbI3 ]0.08 in standard mesoporous PSCs. Remarkable power conversion efficiencies of 17.48 % and 18.30 % were measured for DTTX-1 and DTTX-2, respectively, close to that measured for the benchmarking HTM spiro-OMeTAD (18.92 %), under 100 mA cm-2 AM 1.5G solar illumination. PSCs with DTTX-3 reached a PCE value of 12.68 %, which is attributed to the poorer film formation in comparison to DTTX-1 and DTTX-2. These PCE values are in perfect agreement with the conductivity and hole mobility values determined for the new compounds and spiro-OMeTAD. Steady-state photoluminescence further confirmed the potential of DTTX-1 and DTTX-2 for hole-transport applications as an alternative to spiro-OMeTAD.

N-Annulated Perylene Bisimides to Bias the Differentiation of Metastable Supramolecular Assemblies into J- and H-Aggregates.

The unique self-assembling features of N-annulated perylene bisimides (PBIs) 1 and 2 are reported. The stability of the aggregates of diester 1, in which no H-bonding interactions are operative, corroborates the significance of long-range van der Waals and dipole-dipole electrostatic interactions in the construction of stable supramolecular assemblies. The incorporation of amide functional groups within the N-annulated PBI in 2 stimulates pathway differentiation to achieve up to three J-type aggregates and a fourth H-type aggregate depending on the experimental conditions. The results presented demonstrate unprecedented levels of control over synthetic supramolecular self-assembly and the rich differentiation that N-annulated PBIs exhibit, opening the door to new, complex, functional supramolecular materials.

Decoding the Consequences of Increasing the Size of Self-Assembling Tricarboxamides on Chiral Amplification.

A complete series of experimental and theoretical investigations on the supramolecular polymerization of chiral (1 and 2) and achiral (3) oligo(phenylene ethynylene) tricarboxamides (OPE-TAs) is reported. The performance of seargents-and-soldiers (SaS) and majority rules (MR) experiments has allowed deriving a full set of thermodynamic parameters, including the helix reversal penalty (HRP) and the mismatch penalty (MMP). The results described illustrate the influence exerted by the number of stereogenic centers per monomeric unit and the temperature on the chiral amplification phenomenon. While the HRP decreases upon decreasing the number of chiral side chains, the MMP follows an opposite trend. The experimental trend observed in MR experiments contrasts with that reported for benzenetricarboxamides (BTAs), for which the chiral amplification ability increases by lowering the number of stereogenic centers or increasing the temperature. Theoretical calculations predict that the rotational angle between adjacent monomeric units in the stack (ca. 18°) gradually decreases when decreasing the number of branched chiral side chains and leads to higher MMP values, in good accord with the experimental trend. The reduction of the rotational angle gives rise to less efficient H-bonding interactions between the peripheral amide functional groups and is suggested to provoke a decrease of the HRP as experimentally observed. In BTAs, increasing the number of stereogenic centers per monomeric unit results in a negligible change of the rotation angle between adjacent units (ca. 65°), and, consequently, the steric bulk increases with the number of chiral side chains, leading to higher MMP values. The data presented herein contribute to shed light on the parameters controlling the transfer and amplification of chirality processes in supramolecular polymers, highlighting the enormous influence exerted by the size of the self-assembling unit on the final helical outcome.

Understanding the affinity of bis-exTTF macrocyclic receptors towards fullerene recognition.

A new series of fullerene receptors based on exTTF macrocycles with alkyl ether chains of increasing length is reported. The novel macrocyclic receptors are able to favourably interact with fullerene C60 through a synergistic combination of π-π, CHπ and nπ noncovalent interactions. We identify that the highest affinity towards C60 recognition is achieved for the host with the tightest fit; that is, the smallest receptor with a cavity large enough to host the buckyball inside (log Ka = 5.2 in chlorobenzene at 298 K). However, besides this expected observation, theoretical calculations evidence that the most stable self-assembling configuration corresponds for all the receptors to an outside-ring binding mode, in which the C60 guest is out of the cavity of the receptor. The higher stability of this configuration results from the smaller deformation energy it implies for the receptor, and allows to explain the experimental trends in the association constants.

A combinatorial approach to improving the performance of azoarene photoswitches.

Azoarenes remain privileged photoswitches - molecules that can be interconverted between two states using light - enabling a huge range of light addressable multifunctional systems and materials. Two key innovations to improve the addressability and Z-isomer stability of the azoarenes have been ortho-substitution of the benzene ring(s) or replacement of one of the benzenes for a pyrazole (to give arylazopyrazole switches). Here we study the combination of such high-performance features within a single switch architecture. Through computational analysis and experimental measurements of representative examples, we demonstrate that ortho-benzene substitution of the arylazopyrazoles drastically increases the Z-isomer stability and allows further tuning of their addressability. This includes the discovery of new azopyrazoles with a Z-isomer thermal half-life of ≈46 years. Such results therefore define improved designs for high performance azo switches, which will allow for high precision optically addressable applications using such components.

Breathing-Dependent Redox Activity in a Tetrathiafulvalene-Based Metal-Organic Framework.

"Breathing" metal-organic frameworks (MOFs) that involve changes in their structural and physical properties upon an external stimulus are an interesting class of crystalline materials due to their range of potential applications including chemical sensors. The addition of redox activity opens up a new pathway for multifunctional "breathing" frameworks. Herein, we report the continuous breathing behavior of a tetrathiafulvalene (TTF)-based MOF, namely MUV-2, showing a reversible swelling (up to ca. 40% of the volume cell) upon solvent adsorption. Importantly, the planarity of the TTF linkers is influenced by the breathing behavior of the MOF, directly impacting on its electrochemical properties and thus opening the way for the development of new electrochemical sensors. Quantum chemical calculations and Raman spectroscopy have been used to provide insights into the tunability of the oxidation potential.

Hierarchy of Asymmetry at Work: Chain-Dependent Helix-to-Helix Interactions in Supramolecular Polymers.

A detailed investigation of the hierarchy of asymmetry operating in the self-assembly of achiral (1) and chiral ((S)-2 and (R)-3) 1,3,5-triphenylbenzenetricarboxamides (TPBAs) is reported. The aggregation of these TPBAs is conditioned by the point chirality at the peripheral side chains for (S)-2 and (R)-3. An efficient helix-to-helix interaction that goes further in the organization of fibrillar bundles is experimentally detected and theoretically supported only for the achiral TPBA 1. The effective interdigitation of the achiral aliphatic side chains produces a social self-sorting to form preferentially heterochiral macromolecular aggregates.