Long-range corrected hybrid functionals for π-conjugated systems: dependence of the range-separation parameter on conjugation length

Long-range corrected (range-separated hybrid) functionals represent a relatively new class of functionals for generalized Kohn-Sham theory that have proven to be very successful, for instance, when it comes to predicting ionization potentials and energy gaps for a wide range of molecules and solids. The results obtained from long-range corrected density functional theory approaches can be improved dramatically, if the range-separation parameter (ω) is optimized for each system separately. In this work, we have optimized ω for a series of π-conjugated molecular systems of increasing length by forcing the resulting functionals to obey the ionization potential-theorem, i.e., that their highest occupied eigenvalue be equal to the ΔSCF ionization potential. The optimized ω values are observed to vary substantially from their default values for the functionals. For highly conjugated chains such as oligoacenes and polyenes, we find that the characteristic length scale of the range-separation, i.e., 1/ω, grows almost linearly with the number of repeat units, for saturated alkane chains, however, 1/ω quickly saturates after 5-6 repeat units. For oligothiophenes, we find that 1/ω grows linearly for the shorter oligomers but then saturates at around 10 repeat units. Our results point to a close relation between the optimal range-separation parameter and the degree of conjugation in the system.     

Dimensionally oriented redox-active π-conjugated systems

Porphyrins bearing the redox-active phenylenediamine pendant groups are synthesized to afford dimensionally oriented π-conjugated systems. The structural and electronic characteristics depend on the atropisomers. In the fluorescence emission spectra, the emission from the porphyrin moiety is almost completely quenched. Zinc complexation of the αααα isomers gives the corresponding zinc porphyrins bearing four phenylenediamine strands. Treatment with a bidentate ligand, DABCO, leads to the sandwich dimer complex, in which the porphyrin moieties are surrounded by π-conjugated pendant groups. p-t-Butylcalix[4]arenes bearing four redox-active phenylenediamine pendant groups on the lower rim are synthesized and characterized both spectroscopically and electrochemically. The interconversion of the oxidation states of the pendant groups is demonstrated both chemically and electrochemically.     

Rhodium-catalyzed hydrothiolation of alkynes with thiols for construction of sulfur-containing π-conjugated systems

To synthesize sulfur-containing π-conjugated polymers, reaction conditions for rhodium-catalyzed hydrothiolation of terminal alkynes with arenethiols are optimized in detail. Under the optimized conditions, rhodium-catalyzed hydrothiolation of terminal alkynes proceeds regio- and stereoselectively to afford the corresponding vinyl sulfides via an anti-Markovnikov and syn-addition process. Then, the rhodium-catalyzed hydrothiolation is applied to polymerization of 2,5-diethynylthiophene with benzene-1,4-dithiol, which successfully provides sulfur-containing π-conjugated polymers with excellent regio- and stereoselectivities.     

Electron correlation effects on the first hyperpolarizability of push-pull π-conjugated systems

The first hyperpolarizability (β) of representative push-pull π-conjugated compounds has been calculated at several levels of approximation to assess the effects of electron correlation. First, the 6-31+G(d) basis set has been shown to give the best balance between accuracy and computational resources for a polyene linker whereas for polyyne linker, the 6-31G(d) basis set is already an optimal choice. As a result of cancellations between higher order contributions, the MP2 method turns out to be the method of choice to predict β of push-pull π-conjugated systems since it closely reproduces the values obtained with the reference CCSD(T) scheme. Moreover, the SDQ-MP4 and CCSD approaches provide rarely improved estimates over MP2 while the MP4 method does not represent an improvement over MP4-SDQ or the SCS-MP2 method, over MP2. Among density functional theory exchange-correlation functionals, LC-BLYP is reliable when characterizing the changes of first hyperpolarizability upon enlarging the π-conjugated linker or upon changing the polyyne linker into a polyene segment. Nevertheless, its reliability is very similar to what can be achieved with the Hartree-Fock method and the MP2 scheme is by far more accurate. On the other hand, the BLYP, B3LYP, and BHandHLYP functionals perform quantitatively better in a number of cases but the trends are poorly described. This is also the case of the B2-PLYP and mPW2-PLYP functionals, which are often the most accurate, though they underestimate the increase of β when going from polyyne to polyene linkers and overestimate the enhancement of β with chain length.     

DNA-templated assembly of dyes and extended π-conjugated systems

This feature article reports on the use of DNA as a template to assemble dyes and π-conjugated systems with the aim to construct functional multicomponent nanostructures that have a well-defined size, shape and sequence.     

Spectroscopic probes with changeable π-conjugated systems

Spectroscopic probes have been extensively investigated and used widely in many fields because of their powerful ability to improve analytical sensitivity, and to offer greater temporal and spatial resolution (in some cases a molecule event may be visualized by the naked eye). So far, different photophysical mechanisms, such as charge transfer, photo-induced electron transfer and fluorescent resonance energy transfer, have been employed to develop various spectroscopic probes with superior properties. However, these photophysical mechanisms depend on the energy levels of molecular orbitals, which are usually difficult to accurately determine. This would lead to the poor prediction of analytical performance of the designed probe. Instead, the change of π-conjugated systems induced by chemical reactions is often accompanied by a distinct alteration in spectroscopic signal, which is more predictable and is of high signal/background ratio. This mechanism can serve as an effective measure for developing excellent spectroscopic probes, but to our knowledge, has not been systematically summarized. In this feature article, we review the development of spectroscopic probes with changeable π-conjugated systems, which is catalogued according to the fluorochromes: fluorescein, rhodamine, spiropyran, squaraine, coumarin, cyanine, etc. Two main strategies for constructing these spectroscopic probes, including ring-closing reaction and nucleophilic addition reaction, are summarized, and the merits and limitations of the probes are discussed.     

Recent advances with π-conjugated salen systems

Schiff base ligands have long been successfully employed as ligands in combination with various metals to give catalysts capable of realizing a variety of synthetic transformations. One of the most widely used Schiff base ligands, the "salen" ligand, has been extensively researched. Recently, there has been increased interest in π-conjugated salen systems, known as "salphen" ligands, as a result of the differences in reactivity of the complexes in catalytic applications compared with the salen analogues. Complexes of salphen ligands display interesting photophysical and supramolecular properties which are not always observed with salen systems as a result of their π-conjugation. This tutorial review therefore describes the most significant advances recently made with salphen and related π-conjugated ligand systems.     

Solid-phase Pd-catalysed cross-coupling methods for the construction of π-conjugated peptide nanomaterials

We describe the development of two procedures for the synthesis of peptides that are embedded with a variety of π-conjugated semi-conducting oligomers. These procedures utilise solid-phase variants of classical palladium-catalysed cross-couplings commonly used to prepare π-conjugated oligomers. The resulting peptide–π–electron hybrids are soluble in aqueous media and self-assemble to produce 1D nanostructures, simultaneously forming networks of π-stacked conduits. The procedures have allowed for the inclusion of complex chromophores including mixed aryl units, ethynylene linkers and sexithiophenes where the latter peptide's nanostructures demonstrated substantial conductivity when employed as an active layer in a field-effect transistor.     

Topography of scalar fields: molecular clusters and π-conjugated systems

The pioneering works due to Bader and co-workers have generated widespread interest in the study of the topography of molecular scalar fields, the first step of which is the identification and characterization of the corresponding critical points (CPs). The topography of a molecular system becomes successively richer in going from the bare nuclear potential (BNP) to the molecular electrostatic potential (MESP) through the molecular electron density (MED). The present work clearly demonstrates, through the study of some π-conjugated test molecules as well as molecular clusters, that the CPs could be economically located by following this path within ab initio level theory. Further, the topography mapping of large molecules, especially at a higher level of theory, is known to be a demanding task. However, it is rendered possible by following the above sequential mapping assisted by a divide-and-conquer-type method termed as the molecular tailoring approach (MTA). This is demonstrated with the topography mapping of β-carotene and benzene nonamer at MP2 and a (H(2)O)(32) cluster at the HF level of theory, which are rather challenging problems with contemporary off-the-shelf computer hardware.     

N-heterocyclic carbene boranes as electron-donating and electron-accepting components of π-conjugated systems

Give and take: The introduction of NHC-borane moieties to thiophene-based π?skeletons endows a zwitterionic character, which makes the π?system electron-donating, while the NHC ring acts as an electron-accepting moiety. The NHC-borane-substituted thiophene underwent a clean photoisomerization with a drastic color change, however, the expanded bithiophene derivatives were inert to this photoreaction, showed low oxidation potentials, and formed a slipped π-stacked array in the crystal.     

First-principles approach to the understanding of π-conjugated organic semiconductors

We show how ab initio calculations based on density functional theory contribute to the understanding of the electronic and optical properties of organic semiconducting materials, which form the active layers in many opto-electronic applications. As a textbook example, we present the electronic structure and the optical properties of the oligo-phenylenes as evolving from their benzene-constituents. Thereby we discuss the dependence on the molecular length and introduce the modifications in the opto-electronic properties due to intermolecular interactions which are inherently present in the bulk phase.     

Triphenylamine/tetracyanobutadiene-based D-A-D π-conjugated systems as molecular donors for organic solar cells

Thiophene-based D-A-D π-conjugated systems containing triphenylamine end groups connected to a 1,1,4,4-tetracyanobuta-1,3-diene acceptor by oligothiophene chains of variable length have been synthesized. These compounds show interesting light-harvesting properties and low-lying HOMO levels. Preliminary results on bilayer heterojunction solar cells with C(60) as acceptor show power conversion efficiency higher than 1.0%.     

Quantum-coherence and correlations in π-conjugated molecules and multichromophoric systems

Chemistry is intrinsically founded on quantum mechanical principles and examples of quantum-mechanical phenomena abound on a range of energy and length scales. In this article some examples of quantum-mechanical phenomena that can be probed by optical spectroscopy are discussed. Recent experimental studies of quantumcoherence in electronic energy transfer in π-conjugated polymers are reported as examples of weak correlations. The nature of the electron-hole binding energy for excitons in organic systems is investigated as a case of intermediate correlations. Possible experimental probes of strong correlations involved in chemical reactions are critically examined in the final section of the paper.     

Synthesis and anticancer activity of new azo compounds containing extended π-conjugated systems

A series of novel azo compounds with extended π-conjugated systems were prepared by azo coupling reaction compounds trans-2-(4′-aminostyryl)-thiophene, 1-(4-aminophenyl)-4-phenyl-1,3-butadiene and 4-amino-4′-methoxystilbene with some phenols. The compounds were evaluated for their cytotoxicity against breast cancer adenocarcinoma (MCF-7), cervix adenocarcinoma (HeLa) and human embryonic kidney (HEK 293) cell lines using the MTT assay. The results showed all derivatives had more toxic effects than tamoxifen. Of all the compounds tested, the azo product obtained from coupling trans-2-(4′-Aminostyryl)-thiophene with 2-naphthol (compound 5b) exhibited the potent in vitro antiproliferative activity with IC₅₀ 27 ± 1 and 18 ± 0 µg/mL against MCF-7 and HeLa cell lines, respectively, while it was devoid of any cytotoxicity against normal HEK 293 cells even at 200 µg/mL.     

End-functionalized π-conjugated oligomeric materials for photoelectrical applications

Soluble poly(diphenylacetylene)s (PDA) capped with PhCO- groups (PDA-C) and Ph₂C= groups (PDA-P) were prepared via McMurry reductive coupling of benzil and carbonyl-olefin exchange reaction of tetraphenylethene and benzil, respectively. Fluoren-9-ylidene groups have been introduced into PDA by the McMurry coupling of PDA-C with fluoren-9-one and via copolymerization of benzil and fluoren-9-one. The oligomers prepared are stable in air, soluble in a variety of solvents. They can be processed by casting to form good-quality thin films suitable for measurements of electrical and optoelectrical properties.     

Synthesis and characterization of novel (oligo)thienyl-imidazo-phenanthrolines as versatile π-conjugated systems for several optical applications

A series of new heterocyclic chromophores 3-6 were synthesized in moderate to excellent yields by condensation of 5,6-phenantroline-dione with formyl-thiophene derivatives 1-2 in the presence of ammonium acetate in glacial acetic acid. These chromophores possess an (oligo)thienyl π-conjugated system attached to an imidazo-phenanthroline moiety. These derivatives were evaluated concerning their solvatochromic properties, thermal stabilities, and molecular optical nonlinearities.     

Reviewing extrapolation procedures of the electronic properties on the π-conjugated polymer limit

In this article, the extrapolation procedures of π-π* electronic transition energy on π-conjugated oligomers are reexamined. Different models, including the simplest coupled oscillator, the free electron, the Hückel approach, the molecular exciton model, and some specific fitting-functions, are compared using the transition energies derived from theoretical calculations on three thiophene-based oligomer series. Specifically, oligomers of up to 30 repeating units have been considered to include the saturation effects as a function of chain length. The coupled oscillator model of W. Kuhn and the fitting-function of Hirayama are the models that present the better suit on the transition energy interpolation as a function of chain length. Using only the first four oligomers of the series (n = 2 up to 8) yields an estimation of the transition energy on the polymer limit with an average error of ～1.5%. The vertical and adiabatic ionization potential present a better fit with the Hückel model approach. Finally, implications of the environmental polarity on the electronic properties, molecular geometry, charge distribution, and aromaticity are shortly discussed.     

Unsymmetrically substituted 9,10-dihydro-9,10-diboraanthracenes as versatile building blocks for boron-doped π-conjugated systems

The targeted hydrolysis of the 9,10-dihydro-9,10-diboraanthracene adduct (Me(2)S)HB(C(6)H(4))(2)BH(SMe(2)) (1) with 0.5 equiv of H(2)O leads to formation of the borinic acid anhydride [(Me(2)S)HB(C(6)H(4))(2)B](2)O (2) and thereby provides access to the field of unsymmetrically substituted 9,10-dihydro-9,10-diboraanthracenes. Compound 2 reacts with tBuC≡CH to give the corresponding vinyl derivative in an essentially quantitative conversion. Subsequent cleavage of the B-O-B bridge by LiAlH(4) with formation of hydridoborate functionalities is possible but is accompanied by partial B-C(vinyl) bond degradation. This situation changes when the related mesityl derivative [MesB(C(6)H(4))(2)B](2)O (7) is employed, which can be synthesized from BrB(C(6)H(4))(2)BBr (6) by treatment with 1 equiv of MesMgBr and subsequent hydrolysis. The reaction of 7 with LiAlH(4) in tetrahydrofuran (THF) furnishes Li[MesB(C(6)H(4))(2)BH(2)] (8); hydride elimination with Me(3)SiCl leads to formation of the THF adduct MesB(C(6)H(4))(2)BH(THF) (9·THF). Alternatively, 7 can be transformed into the bromoborane MesB(C(6)H(4))(2)BBr (10) by treatment with BBr(3). A Br/H-exchange reaction between 10 and Et(3)SiH yields the donor-free borane MesB(C(6)H(4))(2)BH (9), which forms B-H-B bridged dimers (9)(2) in the solid state. The vinyl borane MesB(C(6)H(4))(2)BC(H)=C(H)Mes (14) is accessible from MesC≡CH and either 9·THF or 9. Compared with the related compound Mes(2)BC(H)=C(H)Mes, the electronic absorption and emission spectra of 14 reveal bathochromic shifts of Δλ(abs)=17 nm and Δλ(em)=74 nm, which can be attributed to the rigid, fully delocalized π framework of the [MesB(C(6)H(4))(2)B] chromophore.     

Titanylation and vanadylation of highly π-conjugated porphyrins

We report the efficient synthesis of tetrabicycloporphyrin titanyl and vanadyl without decomposition of the bicyclo[2.2.2]octadiene unit. The complexes were heated under vacuum to give titanyl and vanadyl tetrabenzoporphyrins in 100% yield. We also titanylated and vanadylated tetra[2,3]naphthoporphyrin and tetra[2,3]anthraporphyrin, which have a greater degree of π conjugation than tetrabenzoporphyrin.