Fast intramolecular charge transfer with a planar rigidized electron donor/acceptor molecule

The planar rigidized molecule fluorazene (FPP) undergoes fast reversible intramolecular charge transfer (ICT) in the excited state, with a reaction time of 12 ps in the polar solvent ethyl cyanide at -45 degrees C. The ICT state of FPP has a dipole moment mu(e)(ICT) of 13 D, much larger than that of the locally excited state LE (1 D). The ICT behavior of FPP is similar to that of its flexible counterpart N-phenylpyrrole (PP), for which mu(e)(ICT) = 12 D. These results show that intramolecular charge transfer to a planar ICT state can occur efficiently. In designing ICT systems capable of rapid switching, it is therefore important to realize that large amplitude motions such as those necessary for the formation of a twisted intramolecular charge transfer (TICT) state are not required.     

Liquid crystalline copolymers containing electron donor and acceptor mesogens with a chiral group in the spacer unit

Side-chain liquid crystalline polymers containing both mesogenic (carbazolylmethylene)aniline and (4′-nitrobenzylidene)aniline units with various spacer groups were prepared to examine effects of the structure of spacer groups on the liquid crystalline properties. The copolymer containing (R)-(+)-2-methylpropylene as a chiral group in the spacer unit induced a smectic phase; the copolymer with a trimethylene spacer of similar length to the chiral spacer exhibited a nematic phase. Smectic phases were observed for the copolymer containing the chiral spacer group when the proportion of the carbazolyl group was in the range of 0.55–0.88. For example, the copolymer with the proportion of the carbazolyl group of 0.68 expressed the smectic phase from 88° to 167°C. This isotropic temperature was 37° higher than the calculated value (130°C) based on an assumed copolymer composition without the electron donor–acceptor interaction. Thus, it is assumed that for the chiral copolymer containing both electron donor and acceptor groups, the thermal stability and the induction of the smectic phase were caused by both the electron donor–acceptor interaction and the existence of the chiral group in the spacer unit. © 1995 John Wiley & Sons, Inc.     

Transient excitation behavior of a donor–acceptor–acceptor Auger molecule in a semiconductor host

Under the particular situation of highly doped and almost compensated semiconductors, a new kind of bound state happens at high external excitation levels, which is formed of a close donor–acceptor molecule and a neighboring second donor or acceptor. The de-excitation behavior of such a bound state resembles characteristics known from Auger transitions and for this reason it is called an Auger molecule. The existence region of Auger molecules is determined in silicon-doped Ga_{1− x} Al _x As by electron-beam excited luminescence measurements at low temperature. The main peak position and the luminescence intensity of the donor–acceptor recombination channel turn out to be affected in a characteristic manner by the existence of Auger molecules at high excitation levels. An analysis of corresponding rate coefficients for the reproduction of experimental results is also presented. Received: 14 September 1999 / Accepted: 3 February 2000 / Published online: 21 June 2000     

Photonic switching of photoinduced electron transfer in a dithienylethene-porphyrin-fullerene triad molecule

A dithienylethene (DTE)-porphyrin (P)-fullerene (C(60)) triad molecule in which intramolecular photoinduced electron transfer is controlled by the photochromic DTE moiety has been prepared. Irradiation of the molecule with visible light gives the open form of the dithienylethene (DTEo). Excitation of the porphyrin gives DTEo-(1)P-C(60), which undergoes photoinduced electron transfer with a time constant of 25 ps to generate DTEo-P(.+)-C(60)(.-). Irradiation with ultraviolet light produces the closed form of the dithienylethene (DTEc). Excitation of DTEc-P-C(60) yields DTEc-(1)P-C(60), whose porphyrin first excited singlet state is quenched in 2.3 ps by singlet-singlet energy transfer to DTEc, generating (1)DTEc-P-C(60) and precluding significant photoinduced electron transfer. Such highly reversible photonically controlled intramolecular photoinduced electron transfer may eventually be useful in the design of photonic or optoelectronic devices.     

Synthesis of a triad molecular system containing the photosensitizer mesoporphyrin II and a secondary electron donor and acceptor for modeling the photosynthesis process

We describe two methods for synthesis of a trial molecular system based on mesoporphyrin II with electrodonor and electron-acceptor moieties for modeling the primary stage of charge separation in photosynthesis, differing in the order of addition of the donor and the acceptor. Using fluorescent spectroscopy, we have demonstrated quenching-containing compounds. Investigation of the triad and its zinc complex by kinetic fluorescent spectroscopy allowed us to determine the electron transfer rate constants for the triad and for its zinc complex.M. V. Lomonosov State Academy of Fine Chemical Technology, Moscow 117571. Research Institute of Innovative Technology for the Earth, Kyoto 619-02, Japan. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 343–350, March, 1995. Original article submitted December 10, 1994.     

Conjugated alternating copolymers containing both donor and acceptor moieties in the main chain

A straightforward synthesis toward two conjugated alternating copolymers consisting of 2,7-linked carbazole donor (2,7-Cz) and ladderized pentaphenylene with diketone bridge (LPPK) acceptor chromophores is reported: the copolymers differ by the repeat unit ratio between the 2,7-Cz and LPPK units within the backbone; energy and charge transfer properties and supramolecular organizations of donor-acceptor moieties in these copolymers have been studied via optical spectroscopy and two-dimensional wide-angle X-ray scattering (2D-WAXS); preliminary results such as the efficient energy and charge transfer and pi-stacking character in the solid state suggest that the copolymers are potentially useful for photovoltaic devices.     

A theoretical study of the interactions of NF(3) with neutral ambidentate electron donor and acceptor molecules

A theoretical study of the complexes (dimers and trimers) formed between nitrogen trifluoride (NF(3)) and the ambidentate electron donor/acceptor systems HF, FCl, HCN, and HNC has been carried out using DFT [M05-2x/6-311++G(d,p)] and ab initio methods [(MP2/6-311++G(d,p) and MP2/aug-cc-pVTZ)]. Due to its structure, the NF(3) molecule can interact with both electron acceptors and electron donors through its N and F atoms. Thus, five minimum energy structures have been located for the dimers and four minima structures have been studied for the trimer complexes. New σ-hole bonding complexes have been located.     

Photochemical reaction of gadolinium(III) tetraphenylporphyrin in toluene solution containing an electron acceptor or donor

In this paper we have studied by absorption spectroscopy the course of the steady state photolysis of gadolinium(III) complex with 5,10,15,20-tetraphenylporphyrin. The result has been compared with the photolysis of free base tetraphenylporphyrin. Irradiation of GdTPP(acac) and H₂TPP (H₂TPP ≡ tetraphenylporphyrin; Hacac ≡ acetylacetone) with visible light in the presence of triethylamine as an electron donor, leads to their photoreduction. Formation of the gadolinium tetraphenylchlorin complex and tetraphenylchlorin is observed. The process of irradiation in the presence of CCI₄ as an electron acceptor has different pathways for GdTPP(acac) and H₂TPP. The gadolinium complex is mono oxidized, giving rise to the π⁺ radical cation while, for unmetallated porphyrin, dication H₄(TPP)²⁺ formation is observed.     

New [(D-terpyridine)-Ru-(D or A-terpyridine)][4-EtPhCO2]2 complexes (D = electron donor group; A = electron acceptor group) as active second-order non linear optical chromophores

The dipolar and octupolar contributions of the second order nonlinear optical properties of [(4'-(C(6)H(4)-p-D)-2,2':6',2'-terpyridine)-Ru-(4'-(C(6)H(4)-p-A)-2,2':6',2'-terpyridine)]Y(2) heteroleptic complexes (D and A are donor and acceptor groups, respectively), and related free terpyridines and homoleptic complexes, have been obtained by means of a comprehensive combination of Electric Field Induced Second Harmonic generation, Third Harmonic Generation, and Harmonic Light Scattering measurements. These results evidence how a metal can act as a bridge between two π-delocalized terpyridine moieties bearing a D and an A group, respectively, leading to a large quadratic hyperpolarizability hugely dominated by the octupolar contribution.     

Photoinduced electron transfer between a donor and an acceptor separated by a capsular wall

The efficient photoinduced electron transfer from a stilbene derivative incarcerated within a negatively charged organic nanocapsule to positively charged acceptors (methyl viologen and a pyridinium salt) adsorbed outside and the back electron transfer were controlled by supramolecular effects.     

Versatile and practical chiral shift reagent with hydrogen-bond donor/acceptor sites in a macrocyclic cavity

[structure: see text] Bifunctional macrocycle 1 with C2 symmetry was newly synthesized. NMR studies demonstrated that receptor 1 functions as a chiral shift reagent (solvating agent) that is highly effective for a wide range of chiral compounds having a carboxylic acid, oxazolidinone, lactone, alcohol, sulfoxide, sulfoximine, isocyanate, or epoxide functionality. Binding constants were determined to investigate the binding behavior of 1.     

Photoinduced electron transfer in a new Bis(C60)-phthalocyanine triad

[Structure: see text] A novel covalently linked bis([60]fullerene)-phthalocyanine triad is reported, exhibiting long-lived photoinduced charge separation both in solution and in the solid state. The first demonstration of a working solar cell using triad 1 as the active material is also presented.     

Preresonance Raman intensity studies in electron donor/acceptor complexes of tetracyanoethylene

The preresonance Raman intensity enhancement for the ν_C=C and ν_CN vibrations of TCNE complexed with toluene, benzene and fluorobenzene is established. Conclusions regarding the electronic states responsible for the effect are presented.     

Photoelectron spectra of electron donor—acceptor complexes between bromine and alkylamines

The photoelectron spectra of N,N-diethylmethylamine—Br₂, triethylamine—Br₂, tri-n-propylamine—Br₂ and tri-n-butylamine— Br₂ complexes were observed. The n orbitals of the alkylamines as electron donors were found to be stabilized by molecular complex formation, while the σ4p and π4p orbitals of the bromine molecule were destabilized. These results strongly support the charge-transfer mechanism for the complex formation.     

Confining electron donor and acceptor in space to realize high efficiency charge-transfer luminescence

Through-bond charge transfer (CT) could easily occur between an electron donor (D) and an electron acceptor (A),which is fundamental to design various D-A type emissive materials for organic light-emitting diode (OLED) application. Although D-A type emitters have been developed for many years, what makes them in the spotlight is the rise of thermally activated delayed fluorescence (TADF) materials.In 2012, Adachi et al.[1] reported a series of D-A emitters with TADF features to fully utilize electrogenerated excitons. After the pioneer work, numerous TADF materials with D-A structure were extensively explored for the application of organic light emitting diodes (OLEDs)[2].     

Photo-controllable tristability of a dithiolato-bipyridine-Pt(II) complex molecule containing two azobenzene moieties

A new platinum complex with both an azo-bound dithiolato ligand and an azobenzene-bound bipyridine ligand exhibits tristability reversibly controllable using different energy lights.     

Model theory of resonance Raman excitation profiles in electron donor/acceptor complexes

We present a simple theoretical model which qualitatively explains the previously reported unusual features of the resonance Raman (RR) excitation profiles of electron donor/acceptor complexes of TCNE with aromatic donors, in particular the pronounced red-shift of the RR excitation profile vis à vis the absorption spectrum.     

Ionic photodissociation of some polymers quenched with electron donor or acceptor in solution

Ionic photodissociation processes of vinyl polymers with pendant carbazolyl groups in solution have been studied by nonsecond laser photolysis. The ionic dissociation yield decreases in the order of monomer, oligomers, and polymers.     

Solvent effects on the electron donor acceptor complex properties of ferrocene and tetranitromethane

Summary Spectral investigations in the 350–800 nm range of ferrocene (FcH) and tetranitromethane [C(NO₂)₄] solutions in cyclohexane and carbon tetrachloride at concentration-constant (FcH) and variable (tetranitromethane) were made. The electron donor acceptor (EDA) complex of ferrocene and tetranitromethane and its dissociation to the ferricenium cation (FcH⁺) were studied as a function of the solvent, the initial C(NO₂)₄ concentration and reaction time.     

Reversible interchange of charge-transfer versus electron-transfer states in organic electron transfer via cross-exchanges between diamagnetic (donor/acceptor) dyads

The choice of appropriate electron donors (D) and acceptors (A) allows for the first time the simultaneous observation of Mulliken charge-transfer states, [D,A], that can coexist in reversible equilibrium with electron-transfer states, {D+*,A-*}, for various diamagnetic organic redox dyads. The theoretical analysis based on the (two-state) Mulliken-Hush analysis of the intervalence optical transition, together with the spectral identification of the transient ion-radical pairs of D+* and A-*, leads to the construction of the unusual potential-energy surface consisting of a single minimum without any reorganizational barrier for electron-transfer cross-exchanges with driving forces close to the isergonic limit. The mechanistic implications of this direct demonstration of the facile charge-transfer/electron-transfer interchange are discussed.