New Insights into Acylhydrazones E/Z Isomerization: An Experimental and Theoretical Approach.

A family of acylhydrazones have been prepared and characterized with the aim of investigating their potential as information storage systems. Their well-established synthetic methodologies allowed for the preparation of seven chemically stable acylhydrazones in excellent yields that have been photophysically and photochemically characterized. In addition, DFT and TD-DFT calculations have been performed to gain more insights into the structural, energetic and photophysical properties of the E/Z isomers. Our results reveal that E/Z configurational isomerization upon irradiation is highly dependent on the stabilization of the E or Z isomers due to the formation of intramolecular H bonds and the electronic/steric effects intrinsically related to their structures. In addition, Raman spectroscopy is also used to confirm the molecular structural changes after the formation of hydrogen bonds in the isomers.

Tuning the Diradical Character of Indolocarbazoles: Impact of Structural Isomerism and Substitution Position.

In this study, a set of 10 positional indolocarbazole (ICz) isomers substituted with dicyanomethylene groups connected via para or meta positions are computationally investigated with the aim of exploring the efficiency of structural isomerism and substitution position in controlling their optical and electronic properties. Unrestricted density functional theory (DFT), a spin-flip time-dependent DFT approach, and the multireference CASSCF/NEVPT2 method have been applied to correlate the diradical character with the energetic trends (i.e., singlet-triplet energy gaps). In addition, the nucleus-independent chemical shift together with ACID plots and Raman intensity calculations were used to strengthen the relationship between the diradical character and (anti)aromaticity. Our study reveals that the substitution pattern and structural isomerism represent a very effective way to tune the diradical properties in ICz-based systems with meta-substituted systems with a V-shaped structure displaying the largest diradical character. Thus, this work contributes to the elucidation of the challenging chemical reactivity and physical properties of diradicaloid systems, guiding experimental chemists to produce new molecules with desirable properties.

Dynamic Covalent Properties of a Novel Indolo[3,2-b]carbazole Diradical.

This work describes the synthesis and properties of a dicyanomethylene-substituted indolo[3,2-b]carbazole diradical ICz-CN. This quinoidal system dimerises almost completely to (ICz-CN)2 , which contains two long C(sp3 )-C(sp3 ) σ-bonds between the dicyanomethylene units. The minor open-shell ICz-CN component in the solid-state mixture was identified by EPR spectroscopy. Cyclic voltammetry and UV-visible spectroelectrochemical data, as well as comparison with reference monomer ICz-Br reveal that the nature of the one-electron oxidation of (ICz-CN)2 at ambient temperature and ICz-CN at elevated temperature is very similar in all these compounds due to the prevailing localization of their HOMO on the ICz backbone. The peculiar cathodic behaviour reflects the co-existence of (ICz-CN)2 and ICz-CN. The involvement of the dicyanomethylene groups stabilizes the close-lying LUMO and LUMO+1 of (ICz-CN)2 and especially ICz-CN compared to ICz-Br, resulting in a distinctive cathodic response at low overpotentials. Differently from neutral ICz-CN, its radical anion and dianion are remarkably stable under ambient conditions. The UV/Vis(-NIR) electronic transitions in parent (ICz-CN)2 and ICz-CN and their different redox forms have been assigned convincingly with the aid of TD-DFT calculations. The σ-bond in neutral (ICz-CN)2 is cleaved in solution and in the solid-state upon soft external stimuli (temperature, pressure), showing a strong chromism from light yellow to blue-green. Notably, in the solid state, the monomeric diradical species is predominantly formed under high hydrostatic pressure (>1 GPa).

Microwave-assisted functionalization of carbon nanohorns with oligothiophene units with SERS activity.

Carbon nanohorns have been functionalized with oligothiophene units via the 1,3-dipolar cycloaddition reaction under microwave irradiation and solvent-free conditions. A dramatic Raman enhancement was found for one of the synthesized derivatives. Experimental and in silico studies helped to understand the enhancement, attributed to the modification of electromagnetic fields upon functionalization at the tip of the nanostructures.

Push-pull thiophene chromophores for electro-optic applications: from 1D linear to ß-branched structures.

We report the synthesis and characterization of a novel series of push-pull chromophores bearing 1D linear and ß-branched thiophenes as π-conjugated spacers between a 2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline electron donor unit and dicyano- and tricyanovinylene electron acceptor groups. The effect of the introduction of ß-thiophenes on the linear and nonlinear (NLO) optical properties as well as electrochemical and thermal data is studied in detail by performing a comparative study between the branched and 1D linear systems. In addition, a parallel DFT computational study is used to evaluate structure-property relationships. The non-linear optical behavior of the molecules both in solution and in solid state as electro-optic (EO) films using a guest-host approach shows very promising performance for electro-optic applications with high molecular first hyperpolarizabilities (µß) of 4840 × 10-48 esu and electro-optic coefficients r33 reaching 650 pm V-1. One highlight is that the electro-optic films of the ß-branched chromophores are superior in terms of thermal stability in device operation as measured by a transmissive modified reflective Teng-Man method. This work provides guidelines for the design of improved electro-optic materials including ß-branched chromophores which could be useful for practical EO applications, where both enhanced ß and r33 values together with chemical and thermal stability are necessary.

Synthesis of D-A-A and D-A-D Pyrimidine π-Systems Using Triorganoindium Reagents: Optical, Vibrational, and Electrochemical Studies.

A series of donor-acceptor-acceptor (D-A-A) and donor-acceptor-donor (D-A-D) systems based on a pyrimidine π-spacer with various substituents at the C-2 position has been successfully prepared. The synthesis involved site-selective palladium cross-coupling reactions of chloropyrimidines with triorganoindium reagents and proceed in good yields and with atom economy. 4-(N,N-Diphenylamino)phenyl was chosen as the donor group and thien-2-yl dicyanovinylene as the acceptor one. The optical, vibrational, electrochemical, and density functional theory (DFT) calculations of these molecular systems were analyzed, and experimental values show the important role of the substituents at the C-2 position of the pyrimidine with stronger electron accepting ability, absorption in a wide range of UV/vis, acceptable fluorescence lifetime, and effective intramolecular charge transfer (ICT) properties. The ICT was observed in both series by the bathochromic shift on increasing the polarity of the solvent. In addition, DFT calculations found lower lowest unoccupied molecular orbitals of D-A-A molecules that suggest good electron ejection and transportation, being good properties for their application in various organic optoelectronic devices.

Oligothienylenevinylene Polarons and Bipolarons Confined between Electron-Accepting Perchlorotriphenylmethyl Radicals.

A detailed analysis is undertaken of positively charged species generated on a series of thienylenevinylene (nTV) wires terminally substituted with two perchlorotriphenylmethyl (. PTM) radical acceptor groups, . PTM-nTV-PTM. (n=2-7). Motivated by the counterintuitive key role played by holes in the nTV bridges on the operating mechanism of electron transfer in their radical anion mixed-valence derivatives, a wide combination of experimental and theoretical techniques is used, with the aim of gaining further insights into their structural location. Consequently, contributions of the . PTM units for the stabilization of the radical cations and hole localization, particularly in the case of the shortest molecular wire, are probed. In this sense, the formation of quinoidal ring segments, resulting from the coupling of the unpaired electron of the . PTM radical site with those generated along the nTV chains is found. Additionally, open-shell dications, described by the recovery of the central aromaticity and two terminal quinoidal segments, assisted by the . PTM units, are detected.

Poly(thieno[3,4-b]pyrazine-alt-2,1,3-benzothiadiazole)s: A New Design Paradigm in Low Band Gap Polymers.

A new design paradigm for the production of low band gap polymers is reported, in which an ambipolar unit exhibiting both donor and acceptor properties is combined with a conventional acceptor. As initial examples of this approach, the synthesis of two alternating copolymers of thieno[3,4-b]pyrazine and 2,1,3-benzothiadiazole via direct arylation polymerization is reported to give soluble, processable materials with band gaps of 0.97 and 1.05 eV. Although direct arylation polymerization has been previously used to synthesize donor-acceptor materials with band gaps below 1.5 eV, this represents only the second material generated by this polymerization method with a band gap below 1.0 eV.

High-Pressure Chemistry and the Mechanochemical Polymerization of [5]-Cyclo-p-phenylene.

Evidence for the surprising formation of polymeric phases under high pressure for conjugated nanohoop molecules was found. This paper represents one of the unique cases, in which the molecular-level effects of pressure in crystalline organic solids is addressed, and provides a general approach based on vibrational Raman spectroscopy combining experiments and computations. In particular, we studied the structural and supramolecular chemistry of the cyclic conjugated nanohoop molecule [5]cyclo-para-phenylene ([5]CPP) under high pressures up to 10 GPa experimentally and up to 20 GPa computationally. The theoretical modeling for periodic crystals predicts good agreements with the experimentally obtained Raman spectra in the molecular phase. In addition, we have discovered two stable polymeric phases that arise in the simulation. The critical pressures in the simulation are too high, but the formation of polymeric phases at high pressures provides a natural explanation for the observed irreversibility of the Raman spectra upon pressure release between 6 and 7 GPa. The geometric parameters show a deformation toward quinonoid structures at high pressures accompanied by other deformations of the [5]CPP nanohoops. The quinonoidization of the benzene rings is linked to the systematic change of the bond length alternation as a function of the pressure, providing a qualitative interpretation of the observed spectral shifts of the molecular phase.

New Multiresponsive Chromic Soft Materials: Dynamic Interconversion of Short 2,7-Dicyanomethylenecarbazole-Based Biradicaloid and the Corresponding Cyclophane Tetramer.

This work reports on a quinodimethane-type molecule, 2,7-dicyanomethylene-9-(2-ethylhexyl)carbazole (1), one of the shortest π-conjugated biradicaloids reported to be stable in solution under ambient conditions. This carbazole-based quinoidal precursor is able to form a macrocyclic σ-bonded tetramer (2). The resolved single-crystal X-ray structure of tetramer 2 shows that four molecules of 1 are linked together through four long (CN)2 C-C(CN)2 bonds (1.631 Å) resulting from coupling of the unpaired electrons in biradicaloid 1. Dynamic interconversion between monomer 1 and cyclophane tetramer 2 is achieved by reversible cleavage and recovery of the four (CN)2 C-C(CN)2 bonds upon soft external stimuli (light absorption, temperature and pressure), which is accompanied by significant color changes. These novel photo-, thermo-, and mechanochromic properties expand the versatility of π-conjugated biradicaloid compounds as novel functional materials that, in combination with spin chemistry and dynamic covalent chemistry, can be relevant in molecular machines, sensors, and switches.

Bis(aminoaryl) Carbon-Bridged Oligo(phenylenevinylene)s Expand the Limits of Electronic Couplings.

Carbon-bridged bis(aminoaryl) oligo(para-phenylenevinylene)s have been prepared and their optical, electrochemical, and structural properties analyzed. Their radical cations are class III and class II mixed-valence systems, depending on the molecular size, and they show electronic couplings which are among the largest for the self-exchange reaction of purely organic molecules. In their dication states, the antiferromagnetic coupling is progressively tuned with size from quinoidal closed-shell to open-shell biradicals. The data prove that the electronic coupling in the radical cations and the singlet-triplet gap in the dications show similar small attenuation factors, thus allowing charge/spin transfer over rather large distances.

Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes.

New stilbenoid and thiophenic compounds terminally functionalized with donor-donor, acceptor-acceptor, or donor-acceptor moieties and possessing a central [2.2]paracyclophane unit have been prepared, and their properties interpreted in terms of through-bond and through space π-electron delocalization (i.e., π-conjugations). Based on photophysical data, their excited-state properties have been described with a focus on the participation of the central [2.2]paracyclophane in competition with through-bond conjugation in the side arms. To this end, two-photon and one-photon absorption and emission spectroscopy, as a function of temperature, solvent polarity, and pressure in the solid state have been recorded. Furthermore, charge delocalization through the [2.2]paracyclophane in the neutral state and in the oxidized species (radical cations, dications and radical trications) has been investigated, allowing the elucidation of the vibrational Raman fingerprint of through-space charge delocalization. Thus, a complementary approach to both "intermolecular" excitation and charge delocalizations in [2.2]paracyclophane molecules is shown which can serve as models of charge and exciton migration in organic semiconductors.

Oligomers of cyclopentadithiophene-vinylene in aromatic and quinoidal versions and redox species with intermediate forms.

A new series of π-conjugated oligomers based on the 4,4 dihexyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene vinylene repeating unit has been prepared and characterized by X-ray, electrochemical, spectroscopic (UV-Vis absorption, emission and Raman) and density functional theory methods. The oligomers in their neutral, oxidized and reduced forms have been investigated. The neutral compounds show a longer mean conjugation length than oligothiophenes and oligothiophene-vinylenes and display very rich redox chemistry with the stabilization of polycationic states of which the radical cations and dications are strong NIR absorbers, the latter displaying singlet diradicaloid character. An interesting complementarity between the sequence of aromatic-quinoidal structural segments in the radical cations and dications has been described and interpreted. Two derivatives with the 4,4 dihexyl-4H-cyclopenta[2,1-b:3,4-b']dithiophene vinylene unit, disubstituted either with electron donor, bis(triaryl amino) groups, or acceptors bis(dicyano-methylene) caps enforcing a quinoidal structure in the dithiophene-vinylene bridge, have been also synthesized and characterized. The radical cation of the triarylamine compound and the radical anion of the tetracyano compound similarly display hole and electron charge localization, or confinement, in the nitrogen and dicyano surrounding parts, or class II mixed valence systems, while their dication and dianion species, conversely, are open-shell diradical (i.e., polaron pair) and closed-shell (i.e., bipolaron), respectively. The preparation of these new π-conjugated oligomers gives way to the realization of compounds with new electronic properties and unique structures potentially exploitable in organic electronics.

Quinoidal/Aromatic Transformations in π-Conjugated Oligomers: Vibrational Raman studies on the Limits of Rupture for π-Bonds.

The vibrational Raman spectra of several series of aromatic and quinoidal compounds have been analyzed considering the downshifts and upshifts of the frequencies of the relevant Raman bands as a function of the number of repeating units. Oligothiophenes, oligophenylene-vinylenes, and oligoperylenes (oligophenyls) derivatives are studied in a common context. These shifts are taken as spectroscopic fingerprints of the changes in π-conjugation. For a given family, aromatic and quinoidal oligomers have been studied together, and according to their Raman frequency shifts located in the two-well BLA-energy curve of their ground electronic state as a function of the bond-length-alternation pattern (BLA). The connection among BLA values, π-conjugation, and Raman frequencies is taken here as the basis of the study. These Raman shifts/BLA changes have been related to important electronic properties of these one-dimensional linear π-electron delocalized systems such as quinoidal (polyene) and aromatic characters.

Operative Mechanism of Hole-Assisted Negative Charge Motion in Ground States of Radical-Anion Molecular Wires.

Charge transfer/transport in molecular wires over varying distances is a subject of great interest. The feasible transport mechanisms have been generally accounted for on the basis of tunneling or superexchange charge transfer operating over small distances which progressively gives way to hopping transport over larger distances. The underlying molecular sequential steps that likely take place during hopping and the operative mechanism occurring at intermediate distances have received much less attention given the difficulty in assessing detailed molecular-level information. We describe here the operating mechanisms for unimolecular electron transfer/transport in the ground state of radical-anion mixed-valence derivatives occurring between their terminal perchlorotriphenylmethyl/ide groups through thiophene-vinylene oligomers that act as conjugated wires of increasing length up to 53 Å. The unique finding here is that the net transport of the electron in the larger molecular wires is initiated by an electron-hole dissociation intermediated by hole delocalization (conformationally assisted and thermally dependent) forming transient mobile polaronic states in the bridge that terminate by an electron-hole recombination at the other wire extreme. On the contrary, for the shorter radical-anions our results suggest that a flickering resonance mechanism which is intermediate between hopping and superexchange is the operative one. We support these mechanistic interpretations by applying the pertinent biased kinetic models of the charge/spin exchange rates determined by electron paramagnetic resonance and by molecular structural level information obtained from UV-vis and Raman spectroscopies and by quantum chemical modeling.

Modulation of the exfoliated graphene work function through cycloaddition of nitrile imines.

After the feasibility of the 1,3-dipolar cycloaddition reaction between nitrile imines and exfoliated graphene by density functional theory calculations was proved, very few-layer graphene was effectively functionalized using this procedure. Hydrazones with different electronic properties were used as precursors for the 1,3-dipoles, and microwave irradiation as an energy source enabled the reaction to be performed in a few minutes. The anchoring of organic addends on the graphene surface was confirmed by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis. Ultraviolet photoelectron spectroscopy (UPS) was used to measure the work function and band gap of these new hybrids. Our results demonstrate that it is possible to modulate these important electronic valence band parameters by tailoring the electron richness of the organic addends and/or the degree of functionalization.

Iron Alkynyl Helicenes: Redox-Triggered Chiroptical Tuning in the IR and Near-IR Spectral Regions and Suitable for Telecommunications Applications.

The combination of a bis-alkynyl-helicene moiety with two iron centers leads to novel electroactive species displaying unprecedented redox-triggered chiroptical switching. Upon oxidation, strong changes of vibrational modes (either local or extended coupled modes) are detected by vibrational circular dichroism and Raman optical activity. Remarkably, the sign of the optical rotation at 1.54 µm (that is, at wavelengths typically used for telecommunications) changes upon oxidation while the topology and stereochemistry of the helicene remain unchanged.

Benzo-thia-fused [n]thienoacenequinodimethanes with small to moderate diradical characters: the role of pro-aromaticity versus anti-aromaticity.

Open-shell singlet diradicaloids have recently received much attention due to their unique optical, electronic and magnetic properties and promising applications in materials science. Among various diradicaloids, quinoidal π-conjugated molecules have become the prevailing design. However, the need for a fundamental understanding on how the fusion mode and pro-aromaticity/anti-aromaticity affect their diradical character and physical properties remains unaddressed. In this work, a series of pro-aromatic benzo-thia-fused [n]thienoacenequinodimethanes (Thn-TIPS (n = 1-3) and BDTh-TIPS) were synthesized and compared with the previously reported anti-aromatic bisindeno-[n]thienoacenes (Sn-TIPS, n = 1-4). The ground-state geometric and electronic structures of these new quinoidal molecules were systematically investigated by X-ray crystallographic analysis, variable temperature NMR, ESR, SQUID, Raman, and electronic absorption spectroscopy, assisted by DFT calculations. It was found that the diradical character index (y0) increased from nearly zero for Th1-TIPS to 2.4% for Th2-TIPS, 18.2% for Th3-TIPS, and 38.2% for BDTh-TIPS, due to the enhanced aromatic stabilization. Consequently, with the extension of molecular size, the one-photon absorption spectra are gradually red-shifted, the two-photon absorption (TPA) cross section values increase, and the singlet excited state lifetimes decrease. By comparison with the corresponding anti-aromatic analogues Sn-TIPS (n = 1-3), the pro-aromatic Thn-TIPS (n = 1-3) exhibit larger diradical character, longer singlet excited state lifetime and larger TPA cross section value. At the same time, they display distinctively different electronic absorption spectra and improved electrochemical amphotericity. Spectroelectrochemical studies revealed a good linear relationship between the optical energy gaps and the molecular length in the neutral, radical cationic and dicationic forms. Our research work discloses a significant difference between the pro-aromatic and anti-aromatic quinoidal compounds and provides guidance for the design of new diradicaloids with desirable properties.

The Raman fingerprint of cyclic conjugation: the case of the stabilization of cations and dications in cycloparaphenylenes.

Radical cations and dications of [n]CPP from n = 5 to n = 12 have been studied by Raman spectroscopy and density functional theory. Small [n]CPP dications owe their stability to the closed-shell electronic structure imposed by cyclic conjugation surpassing the destabilizing effect of ring strain and of the electron deficiency of the charged states. Large [n]CPP dications mitigate cyclic strain by forming diradicals. The Raman spectra reflect the balance among cyclic conjugation, cyclic strain and biradicaloid stabilization by finding an unexpected turning point in the frequency behavior of the G vibrational modes as a function of size. These Raman data represent the vibrational fingerprint of this rare form of conjugation which is central to stabilize both cations and dications of [n]CPP macrocycles.

D-π-A Compounds with Tunable Intramolecular Charge Transfer Achieved by Incorporation of Butenolide Nitriles as Acceptor Moieties.

Chromophores where a polyenic spacer separates a 4H-pyranylidene or benzothiazolylidene donor and three different butenolide nitriles have been synthesized and characterized. The role of 2(5H)-furanones as acceptor units on the polarization and the second-order nonlinear (NLO) properties has been studied. Thus, their incorporation gives rise to moderately polarized structures with NLO responses that compare favorably to those of related compounds featuring more efficient electron-withdrawing moieties. Derivatives of the proaromatic butenolide PhFu show the best nonlinearities. Benzothiazolylidene-containing chromophores present less alternated structures than their pyranylidene analogues, and, unlike most merocyanines, the degree of charge transfer does not decrease on lengthening the π-bridge.