Spectroscopic and theoretical studies of optically active porphyrin dimers: a system uninterpretable by exciton coupling theory.

The electronic excited states of a meso-meso beta-beta doubly linked bis-porphyrin are comprehensively investigated by measuring its circular dichroism (CD) and magnetic circular dichroism (MCD) spectra. The observed spectroscopic properties are rationalized by DFT calculations. The frontier molecular orbitals (MOs) are constructed by the linear combinations of the constituent monomers' four MOs. Comparison of a theoretical CD spectrum based on time-dependent DFT (TDDFT) with the experimental spectra resulted in the assignment of the helical conformation of the dimer. This assignment is contrary to the previous assignment based on the point-dipole approximation (exciton coupling theory).     

MAGNETIC CIRCULAR DICHROISM OF BACTERIOCHLOROPHYLL a IN SOLUTION AND IN A PROTEIN

Abstract— The magnetic circular dichroism (MCD) (300–850nm) of the bacteriochlorophyll (Bchl) a -protein from the green photosynthetic bacterium Prosthecochloris aestuarii 2 K is qualitatively similar to the MCD of Bchl a in methanol and ether solution. This result implies that the transition dipole of the lowest energy electronic transition (near 800 nm) is roughly perpendicular to the transition dipole of the next higher electronic band (near 600nm) for Bchl a molecules in the protein just as it is for molecules in solution. This result provides no support for the recent proposal that interactions with the protein rotates the direction of the transition dipoles of the 800nm band of all the Bchl a molecules in the protein by 90°. While a rotation of the 800nm transition dipoles cannot be rigorously excluded, it would be necessary for the postulated perturbation to rotate the transition dipoles of both the 800 and 600nm bands by 90°. In a broader sense, any postulated perturbation would have to be shown to leave both the absorption spectrum and the MCD largely unaffected. MCD is a more sensitive test than absorption spectroscopy for perturbations of electronic states and changes in the relative orientation of transitions, because it depends on both the magnitudes and directions of at least two electric and one magnetic transition dipole.     

Novel chiral pyromellitdiimide (1,2,4,5-benzenetetracarboxydiimide) dimers and trimers: exploring their structure,electronic transitions,and exciton coupling

The chiral but highly symmetrical acyclic and cyclic pyromellitic diimide dimers and trimers 2-5 have been obtained and characterized for the first time. The pyromellitdiimide chromophores in these molecules are linked by a rigid diequatorially 1,2-disubstituted cyclohexane skeleton. The structures of the compounds have been determined in detail by molecular modeling and, in the case of cyclic dimer 4 and trimer 5, by means of X-ray diffraction analysis. The electronically excited states of the pyromellitdiimide chromophore (1a) have been studied in these and other model compounds by means of linear dichroism (LD), magnetic circular dichroism (MCD), and circular dichroism (CD) spectroscopy. CD spectra of the rigid cyclic trimer 5 have provided the most detailed information on the excited states of the pyromellitdiimide chromophore. The low-energy tail (340-360 nm) of the absorption envelope can be assigned to out-of-plane polarized n-pi* transitions (I, II). The higher energy bands are due to contributions from up to six pi-pi* transitions, these being polarized either along the long (IV-VI, VIII) or short axis (III, VII). The results of ab initio CIS/cc-pVDZ and semiempirical INDO/S-CI calculations have been compared with the experimental data. CD Cotton effects in the region 200-260 nm, which result from exciton interactions between electric dipole allowed transitions of two pyromellitdiimide chromophores in compounds 2-5, provide reliable and useful information concerning the conformation and absolute configuration of these molecules, which may be extrapolated to other oligoimide systems.     

Spectroscopic and density functional theory studies of the blue-copper site in M121SeM and C112SeC azurin: Cu-Se versus Cu-S bonding

S K-edge X-ray absorption, UV-vis absorption, magnetic circular dichroism (MCD), and resonance Raman spectroscopies are used to investigate the electronic structure differences among WT, M121SeM, and C112SeC Pseudomonas aeruginosa (P.a) azurin. A comparison of S K-edge XAS of WT and M121SeM azurin and a CuII-thioether model complex shows that the 38% S character in the ground state wave function of the blue-copper (BC) sites solely reflects the Cu-SCys bond. Resonance Raman (rR) data on WT and C112SeC azurin give direct evidence for the kinematic coupling between the Cu-SCys stretch and the cysteine deformation modes in WT azurin, which leads to multiple features in the rR spectrum of the BC site. The UV-vis absorption and MCD data on WT, M121SeM, and C112SeC give very similar C0/D0 ratios, indicating that the C-term MCD intensity mechanism involves Cu-centered spin-orbit coupling (SOC). The spectroscopic data combined with density functional theory (DFT) calculations indicate that SCys and SeCys have similar covalent interactions with Cu at their respective bond lengths of 2.1 and 2.3 A. This reflects the similar electronegativites of S and Se in the thiolate/selenolate ligand fragment and explains the strong spectroscopic similarities between WT and C112SeC azurin.     

Magnetic circular dichroism of I2 in the cordes band energy region

The absorption and magnetic circular dichroism (MCD) of iodine in the gas phase was recorded over the wavelength range 1950-1780 Å. The strong MCD si     

Joint spectroscopic and theoretical investigations of transition metal complexes involving non-innocent ligands

A series of transition metal complexes involving non-innocent o-dithiolene and o-phenylenediamine ligands has been characterized in detail by various spectroscopic methods like magnetic circular dichroism (MCD), absorption (abs), resonance Raman (rR), electron paramagnetic resonance (EPR), and sulfur K-edge X-ray absorption spectroscopies. A computational model for the electronic structure of the complexes is then proposed based on the density functional theory (DFT) or ab-initio methods, which can successfully account for the observed trends in the experimental spectra (MCD, rR, and abs) of the complexes. Based on these studies, the innocent vs non-innocent nature of the ligands in a given transition metal complex is found to be dependent on the position of the central metal ion in the periodic table, its effective nuclear charge in interplay with relativistic effects.     

Definitive assignments of the visible-near-IR bands of porphyrin-naphthalocyanine rare-earth sandwich double- and triple-decker compounds by magnetic circular dichroism spectroscopy

A series of heteroleptic rare-earth sandwich complexes [M(Nc)(OEP)] (M = La, Nd, Eu, Dy, and Lu; Nc = 2,3-naphthalocyaninate; OEP = octaethylporphyrinate) have been investigated by electronic absorption and magnetic circular dichroism (MCD) spectroscopy. The electronic absorption spectra of the neutral forms showed two characteristic transitions (bands I and II) in the near-IR region, both of which were systematically shifted depending on the size of their central metal. In the MCD spectra, a relatively intense Faraday A term and a significantly weak Faraday B term have been observed corresponding to bands II and I, respectively. The spectral features were successfully interpreted using a simple MO model by considering the relevant interactions of Gouterman's four orbitals of the constituent chromophores. The model succeeded in assigning the MCD spectra of the related compounds, the oxidized and reduced forms of the dimer ([M(Nc)(OEP)]+ and [M(Nc)(OEP)]-), and neutral forms of the triple-decker compounds (M2(Nc)(OEP)2, M = Nd, Eu). DFT calculations of the dimers supported the validity of this model.     

Absorption and magnetic circular dichroism spectra of matrix isolated Ta atoms

The absorption and magnetic circular dichroism (MCD) spectra of Ta atoms isolated in an argon matrix at 14 K have been measured. Over sixty-five MCD bands have been observed and used together with gas phase intensity and energy pattern data to reassign the matrix spectrum. The observed matrix shift (average: 765 cm^?1) to the blue is smaller than determined by previous workers. From this study it is suggested that the assignment of matrix-isolated atomic species can be considerably aided by the determination of their magnetic circular dichroism spectra.     

Resolving Electronic Transitions in Synthetic Fluorescent Protein Chromophores by Magnetic Circular Dichroism

The detailed electronic structures of fluorescent chromophores are important for their use in imaging of living cells. A series of green fluorescent protein chromophore derivatives is examined by magnetic circular dichroism (MCD) spectroscopy, which allows the resolution of more bands than plain absorption and fluorescence. Observed spectral patterns are rationalized with the aid of time‐dependent density functional theory (TDDFT) computations and the sum‐over‐state (SOS) formalism, which also reveals a significant dependence of MCD intensities on chromophore conformation. The combination of organic and theoretical chemistry with spectroscopic techniques also appears useful in the rational design of fluorescence labels and understanding of the chromophore's properties. For example, the absorption threshold can be heavily affected by substitution on the phenyl ring but not much on the five‐member ring, and methoxy groups can be used to further tune the electronic levels.     

Magnetic Circular Dichroism and Electronic Spectra of Tropothione

The magnetic circular dichroism (MCD) and electronic absorption spectra of tropothione have been measured. The circular-dichroism (CD) spectrum of the β-cyclodextrin complex with tropothione is also reported. The absorption bands of tropothione are assigned.     

Pigment-pigment and pigment-protein interactions in recombinant water-soluble chlorophyll proteins (WSCP) from cauliflower

Plants contain water-soluble chlorophyll-binding proteins (WSCPs) that function neither as antennas nor as components of light-induced electron transfer of photosynthesis but are likely constituents of regulatory protective pathways in particular under stress conditions. This study presents results on the spectroscopic properties of recombinant WSCP from cauliflower reconstituted with chlorophyll b (Chl b) alone or with mixtures of Chl a and Chl b. Two types of experiments were performed: (a) measurements of stationary absorption spectra at 77 and 298 K and CD spectra at 298 K and (b) monitoring of laser flash-induced transient absorption changes with a resolution of 200 fs in the time domain of up to 100 ps. On the basis of a theoretical analysis outlined by Renger et al. (J. Phys. Chem. B 2007, 111, 10487) the data obtained in part (a) are interpreted within a model where tetrameric WSCP binds predominantly two Chl molecules in the form of an excitonically coupled "open sandwich" dimer with a tilt angle of about 30 degrees between the chlorin planes. The time-resolved measurements on Chl a/Chl b heterodimers are described by two exponential kinetics with time constants of 400 fs and 7 ps. These kinetics are assumed to reflect a heterogeneous population of WSCPs with Chl dimers either in excitonic coupled "open sandwich" or weakly coupled geometric arrays. The 400 fs component is assigned to excited-state relaxations from the upper to the lower excitonic level of the strongly coupled "open sandwich" dimer, while the 7-8 ps component probably indicates excitation energy transfer from 1Chl b* to Chl a in a dimer array with weak coupling due to significantly longer mutual distances between the chlorin rings.     

Probing excitation delocalization in supramolecular chiral stacks by means of circularly polarized light: experiment and modeling

Photoexcitations in helical aggregates of a functionalized, chiral oligophenylenevinylene (MOPV) are described going beyond the Born-Oppenheimer approximation, in the form of dressed (polaronic) Frenkel excitons. This allows for accurate modeling of the experimentally observed wavelength dependence of the circular polarization in fluorescence, which directly probes the non-adiabatic nature of the electron-vibration (EV) coupling in this system. The fluorescence photon is emitted from a nuclear geometry in which one MOPV and its two nearest neighbors have a nuclear equilibrium that differs appreciably from the ground state due to the presence of the excited state. The absorption and emission band shape and the circular dichroism are consistent with a coherence range of the emitting excitation of approximately two neighboring molecules. Random fluctuations in the zero-order excited-state energy of the MOPVs (disorder) limit the exciton delocalization and can be described by a Gaussian distribution of energies with a width sigma=0.12 eV and a spatial correlation length l0 approximately 5 molecules. We find that disorder and EV coupling act synergistically in localizing the emitting exciton to a single MOPV in the aggregate with 95% probability.     

Boronic acid-protected gold clusters capable of asymmetric induction: spectral deconvolution analysis of their electronic absorption and magnetic circular dichroism

Gold clusters protected by 3-mercaptophenylboronic acid (3-MPB) with a mean core diameter of 1.1 nm are successfully isolated, and their absorption, magnetic circular dichroism (MCD), and chiroptical responses in metal-based electronic transition regions, which can be induced by surface D-/L-fructose complexation, are examined. It is well-known that MCD basically corresponds to electronic transitions in the absorption spectrum, so simultaneous deconvolution analysis of electronic absorption and MCD spectra of the gold cluster compound is conducted under the constrained requirement that a single set of Gaussian components be used for their fitting. We then find that fructose-induced chiroptical response is explained in terms of the deconvoluted spectra experimentally obtained. We believe this spectral analysis is expected to benefit better understanding of the electronic states and the origin of the optical activity in chiral metal clusters.     

Application of MCD spectroscopy and TD-DFT to a highly non-planar porphyrinoid ring system. New insights on red-shifted porphyrinoid spectral bands

The first magnetic circular dichroism (MCD) spectra are reported for tetraphenyltetraacenaphthoporphyrin (TPTANP). The impact on the electronic structure of steric interactions between the fused acenaphthalene rings and the meso-tetraphenyl substituents is explored based on an analysis of the optical spectra of the Zn(II) complex (ZnTPTANP) and the free base dication species ([H4TPTANP]2+). In the case of ZnTPTANP, significant folding of the porphyrinoid ligand induces a highly unusual MCD-sign reversal providing the first direct spectroscopic evidence of ligand nonplanarity. Density functional theory (DFT) geometry optimizations for a wide range of Zn(II) porphyrinoids based on the B3LYP functional and TD-DFT calculations of the associated UV-visible absorption spectra are reported, allowing a complete assessment of the MCD data. TPTANP complexes are found to fall into a class of cyclic polyenes, termed as soft MCD chromophores by Michl (J. Pure Appl. Chem. 1980, 52, 1549.), since the signs of the Faraday A1 terms observed in the MCD spectrum are highly sensitive to slight structural changes. The origin of an unusually large red shift of the main B (or Soret) band of MTPTANP (the most red shifted ever reported for fused-ring-expanded metal porphines) and of similar red shifts observed in the spectra of other peripherally crowded porphyrinoid complexes is also explored and explained on this basis.     

Magnetic Circular Dichroism and Induced Circular Dichroism Spectra of N‐Bromophthalimide

The magnetic circular dichroism (MCD), induced circular dichroism (ICD) spectra, and the absorption spectra of N‐bromophthalimide have been measured. The ICD spectrum of the β‐cyclodextrin complex with N‐bromophthalimide is also reported. The absorption bands of N‐bromophthalimide are assigned.     

Circular dichroism of large molecules

The circular dichroism of molecules, which are large compared to the wavelength of light, is considered. Explicit expressions are obtained for the circular dichroism and absorption of an exciton dimer and of a free particle on a helix. The dimensions are described for which the dipole approximation for the optical properties fails.     

Intra- and inter-monomeric transfers in the light harvesting LHCII complex: the Redfield-Förster picture

We further develop the model of energy transfer in the LHCII trimer based on a quantitative fit of the linear spectra (including absorption (OD), linear dichroism (LD), circular dichroism (CD), and fluorescence (FL)) and transient absorption (TA) kinetics upon 650 nm and 662 nm excitation. The spectral shapes and relaxation/migration rates have been calculated using the combined Redfield-F?rster approach capable of correctly describing fast relaxation within strongly coupled chlorophyll (Chl) a and b clusters and slow migration between them. Within each monomeric subunit of the trimeric complex there is fast (sub-ps) conversion from Chl's b to Chl's a at the stromal side accompanied by slow (>10 ps) equilibration between the stromal- and lumenal-side Chl a clusters in combination with slow (>13 ps) population of Chl's a from the 'bottleneck' Chl a604 site. The connection between monomeric subunits is determined by exciton coupling between the stromal-side Chl's b from the two adjacent subunits (Chl b601'-608-609 cluster) making a simultaneous fast (sub-ps) population of the Chl's a possible from both subunits. Final equilibration occurs via slow (>20 ps) migration between the Chl a clusters located on different monomeric subunits. This migration includes up-hill transfers from the red-most Chl a610-611-612 clusters located at the peripheral side in each subunit to the Chl a602-603 dimers located at the inner side of the trimeric LHCII complex.     

光学活性金属卟啉的磁手性效应研究

磁光学活性与自然光学活性均可用介质对左右圆偏振光的吸收之差来表示 .但自然光学活性和磁光学活性的物理机制是截然不同的 ,前者源于镜象不能互相重叠介质的非定域光学响应 ( nonlocaloptical response) ,而后者则是由于介质的时间反演对称性 ( time- reversal symmetry)被磁场打破所致 .理论分析表明 ,当介质的两种光学活性同时存在时 ,将会出现一个新的附加光学效应 ,这种磁光学活性与自然光学活性之间的交叉效应称为磁手性效应 ( magneto- chiral effect)或磁手二色性 ( magneto-chiral dichroism) [1,2 ] .磁手性效应通常很弱 ,直到 1…