Photoswitchable compounds, which can be reversibly switched between two isomers by light, continue to attract significant attention for a wide array of applications. Azoheteroarenes represent relatively new but understudied type photoswitch, where one the aryl rings from conventional azobenzene class has been replaced with five-membered heteroaromatic ring. Initial studies have suggested azoheteroarenes—the arylazopyrazoles in particular—to excellent photoswitching properties (quantitative...

We review progress in the study of electroactive MOFs with redox activity for energy conversion and storage. Recent advances mixed-valence are highlighted, which have led to record conductivities towards metallic porous materials.

Arylazopyrazole derivatives based on four core structures (4pzMe, 3pzH, 4pzH, and 4pzH-F2) functionalized with a dodecanoate group were demonstrated to store thermal energy in their metastable Z isomer liquid phase release the by optically triggered crystallization at -30 °C for first time. Three heat storage-release schemes discovered involving different activation methods (optical, thermal, or combined) generating liquid-state isomers capable of storing energy. Visible light irradiation...

Abstract The unique self‐assembling features of N ‐annulated perylene bisimides (PBIs) 1 and 2 are reported. stability the aggregates diester , in which no H‐bonding interactions operative, corroborates significance long‐range van der Waals dipole–dipole electrostatic construction stable supramolecular assemblies. incorporation amide functional groups within PBI stimulates pathway differentiation to achieve up three J‐type a fourth H‐type aggregate depending on experimental conditions....

Azoarenes remain privileged photoswitches - molecules that can be interconverted between two states using light enabling a huge range of addressable multifunctional systems and materials. Two key innovations to improve the addressability Z-isomer stability azoarenes have been ortho-substitution benzene ring(s) or replacement one benzenes for pyrazole (to give arylazopyrazole switches). Here we study combination such high-performance features within single switch architecture. Through...

The synthesis of two series N-annulated perylene bisimides (PBIs), compounds 1 and 2, is reported, their self-assembling features are thoroughly investigated by a complete set spectroscopic measurements theoretical calculations. study corroborates the enormous influence that distance between PBI core peripheral groups exerts on chiroptical properties supramolecular polymerization mechanism. Compounds 1, with separated from central methylenes an ester group, form J-type polymers in...

Herein, we report on the use of tetrathiavulvalene-tetrabenzoic acid, H4TTFTB, to engender semiconductivity in porous hydrogen-bonded organic frameworks (HOFs). By tuning synthetic conditions, three different polymorphs have been obtained, denoted MUV-20a, MUV-20b, and MUV-21, all them presenting open structures (22, 15, 27%, respectively) suitable TTF stacking for efficient orbital overlap. Whereas MUV-21 collapses during activation process, MUV-20a MUV-20b offer high stability evacuation,...

"Breathing" metal–organic frameworks (MOFs) that involve changes in their structural and physical properties upon an external stimulus are interesting class of crystalline materials due to range potential applications including chemical sensors. The addition redox activity opens up a new pathway for multifunctional "breathing" frameworks. Herein, we report the continuous breathing behavior tetrathiafulvalene (TTF)-based MOF, namely MUV-2, showing reversible swelling (up ca. 40% volume cell)...

Abstract A combination of spectroscopy (UV/Vis absorption, emission, and circular dichroism), microscopy (AFM TEM), computational studies reveal the formation non‐centrosymmetric homochiral columnar subphthalocyanine assemblies. These assemblies form through a cooperative supramolecular polymerization process driven by hydrogen‐bonding between amide groups, π–π stacking, dipolar interactions axial BF bonds.

Abstract Three new star‐shaped hole‐transporting materials (HTMs) incorporating benzotripyrrole, benzotrifuran, and benzotriselenophene central cores endowed with three‐armed triphenylamine moieties ( BTP‐1 , BTF‐1 BTSe‐1 respectively) are designed, synthesized, implemented in perovskite solar cells (PSCs). The impact that the heteroatom‐containing scaffold has on electrochemical photophysical properties, as well photovoltaic performance, is systematically investigated compared their...

A complete series of experimental and theoretical investigations on the supramolecular polymerization chiral (1 2) achiral (3) oligo(phenylene ethynylene) tricarboxamides (OPE-TAs) is reported. The performance seargents-and-soldiers (SaS) majority rules (MR) experiments has allowed deriving a full set thermodynamic parameters, including helix reversal penalty (HRP) mismatch (MMP). results described illustrate influence exerted by number stereogenic centers per monomeric unit temperature...

In this work, we present a thorough assessment of the performance some representative double-hybrid density functionals (revPBE0-DH-NL and B2PLYP-NL) as well their parent hybrid GGA counterparts, in combination with most modern version nonlocal (NL) van der Waals correction to describe very large weakly interacting molecular systems dominated by noncovalent interactions. Prior assessment, an accurate homogeneous set reference interaction energies was computed for supramolecular complexes...

High efficiency (18.1%) perovskite solar cells are demonstrated by using a hole transporting material with very low reorganization energy (<italic>λ</italic>).

Abstract Herein, we investigate the association of a fullerene fragment, hemifullerene C 30 H 12 , with an electron‐donating bowl‐shaped tetrathiafulvalene derivative (truxTTF). UV/Vis titrations and DFT calculations support formation supramolecular complex, for which constant log K =3.6±0.3 in CHCl 3 at room temperature is calculated. Remarkably, electron transfer from truxTTF to form fully charge‐separated species takes place upon irradiation associate light, constituting first example...

Two new conjugated porphyrin-based systems (dimers 3 and 4) endowed with suitable crown ethers have been synthesized as receptors for a fullerene-ammonium salt derivative (1). Association constants in solution determined by UV-vis titration experiments CH2Cl2 at room temperature. The designed hosts are able to associate up two fullerene-based guest molecules present association high ∼5 × 108 M-1. Calculation of the allosteric cooperative factor α supramolecular complexes [3·12] [4·12] showed...

The type and behaviour of point defects in 0D lead halide perovskites is found to be radically different from their 3D counterparts

The behaviour of grain boundaries in polycrystalline halide perovskite solar cells remains poorly understood. Whereas theoretical studies indicate that are not active for electron-hole recombination, there have been observations higher non-radiative recombination rates involving these extended defects. We find iodine interstitial defects, which established as a center bulk crystals, tend to segregate at planar defects CsPbI3. First-principles calculations show enhanced structural relaxation...

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 unique chiroptical properties. However, in contrast more common planar discotics, self-assembly conic or pyramidic solution remains largely unexplored. Here, we how a molecular geometry change, flat conic, can generate supramolecular landscapes where different...

A decade after the report of first efficient perovskite-based solar cell, development novel hole-transporting materials (HTMs) is still one main topics in this research field. Two advance vectors topic lie obtaining with enhanced hole-extracting capability and easing their synthetic cost. The use anthra[1,9-bc:5,10-b'c']dithiophene (ADT) as a flat π-conjugated frame for bearing arylamine electroactive moieties allows two highly HTMs from very cheap precursors. cells fabricated making mixed...

Lead halide perovskite nanocrystals are highly attractive for next-generation optoelectronics because they easy to synthesize and offer great compositional morphological tunability. However, the replacement of lead by tin sustainability reasons is hampered unstable nature Sn2+ oxidation state an insufficient understanding chemical processes involved in synthesis. Here, optimized synthetic route demonstrated obtain stable, tunable, monodisperse CsSnI3 nanocrystals, exhibiting well-defined...

Bond breaking has emerged as a new tool to postsynthetically modify the pore structure in metal-organic frameworks since it allows us obtain environments structures that are inaccessible by other techniques. Here, we extend concept of clip-off chemistry archetypical ZIF-8, taking advantage different stabilities bonds between imidazolate and Zn Fe metal atoms heterometallic Fe-Zn-ZIF-8. We demonstrate centers can be removed selectively without affecting backbone is supported atoms. This...

Abstract The synthesis and characterization of a new Co(II) spin‐crossover (SCO) complex based on 4′‐(4‐carboxyphenyl)−2,2′:6′,2″‐terpyridine ligand are reported. This can be successfully grafted silver surface maintaining the SCO behavior. Thus, atomic force microscopy (AFM), matrix assisted laser desorption ionization – time‐of‐flight mass spectrometry (MALDI‐TOF MS), Raman spectroscopy, XPS measurements, upon deposition, evidence formation monolayer intact molecules through carboxylate...

The role of π-conjugated molecular bridges in through-space and through-bond electron transfer is studied by comparing two porphyrin-fullerene donor-acceptor (D-A) dyads. One dyad, ZnP-Ph-C60 (ZnP = zinc porphyrin), incorporates a phenyl bridge between D A behaves very similarly to analogous dyads previously. second ZnP-EDOTV-C60, introduces an additional 3,4-ethylenedioxythienylvinylene (EDOTV) unit into the conjugated bridge, which increases distance A, but, at same time, provides...

Abstract Arylazopyrazoles show significant potential as next‐generation photoswitches, in particular because of the high thermal stability their Z ‐isomers. Herein we investigate to perform − E isomer chemical switching arylazopyrazoles using acid. We that acid‐accelerated isomerisation allows for robust mild acids and opens up possibility use light‐acid cycles near quantitatively reversibly switch at room temperature. attribute azonium formation, facilitated by mesomeric stabilisation...

Abstract The unique self‐assembling features of N ‐annulated perylene bisimides (PBIs) 1 and 2 are reported. stability the aggregates diester , in which no H‐bonding interactions operative, corroborates significance long‐range van der Waals dipole–dipole electrostatic construction stable supramolecular assemblies. incorporation amide functional groups within PBI stimulates pathway differentiation to achieve up three J‐type a fourth H‐type aggregate depending on experimental conditions....