Milan Gembicky

Capturing and Analyzing the Excited-State Structure of a Cu(I) Phenanthroline Complex by Time-Resolved Diffraction and Theoretical Calculations

Time-resolved crystallography and density functional theory calculations are used to analyze the geometric and electronic changes that occur upon photoexcitation of [Cu(I)(dmp)(dppe)](+) in crystalline [Cu(I)(dmp)(dppe)][PF(6)] [dmp = 2,9-dimethyl-1,10-phenanthroline; dppe = 1,2-bis(diphenylphosphino)ethane]. In the pump-probe experiment, laser and X-ray pulses are synchronized to capture an image of the instantaneous molecular distortions in the transient triplet state. Parallel theoretical calculations, with the phenyl groups replaced by methyl groups, yield information on the distortion of the isolated cation and the change in electron density upon excitation. The experimental distortions are significantly less than the calculated values and are different for the two independent molecules in the asymmetric unit; these findings are attributed to the constraining influence of the crystal matrix. The calculations indicate that the electron transfer upon excitation is mostly from the dmpe ligand to the dmp ligand, while the Cu atomic charge changes by only approximately +0.1e, although the charge distribution on Cu is significantly affected. As found for homoleptic [Cu(I)(dmp)(2)](+), the change in the population of the Cu atom is close to the calculated difference between the corresponding Cu(II) and Cu(I) complexes. Charge density difference maps confirm these conclusions and show a large rearrangement of the electron density on the Cu atom upon excitation.

The structure of short-lived excited states of molecular complexes by time-resolved X-ray diffraction

Experimental and computational methods for time-resolved (TR) diffraction now allow the determination of geometry changes on molecular excitation. The first results indicate significant changes in the interatomic distances and molecular shape on photo-excitation, but also a dependence of the induced changes on the molecular environment. Though the use of high-brightness synchrotron sources is essential, it limits the time resolution to the width of the synchrotron pulse which is currently 70-100 ps. The experiments discussed fall into two categories: (i) picosecond powder diffraction experiments on the molecular excitation to a singlet state, and (ii) microsecond experiments on the excited states of inorganic complexes. Both involve reversible processes for which a stroboscopic technique can be applied.

A fast mechanical shutter for submicrosecond time-resolved synchrotron experiments

A new high-speed high-repetition-rate X-ray beam shutter for time-resolved photocrystallography at synchrotron sources has been developed and tested. The new design is based on a commercially existing DC servomotor and a frequency-lock control capable linear amplifier. Accurate speed control combined with an air bearing results in extremely low jitter in the motor rotation. Measured jitter at rotation speeds of 12000 to 30000 r min-1 is less than 2 ns at a 6sigma confidence level. The chopper disc is interchangeable, allowing maximum flexibility. The chopper disc currently installed has 45 radial slots which allows synchronization from the 12th to the 20th subfrequencies of the orbit frequency of the Advanced Photon Source storage ring, corresponding to X-ray pulse frequencies of 13.6 to 22.6 kHz. At 30000 r min-1 the opening time window with a 350 microm slot size is 2.11 micros, and correspondingly less with smaller openings, which may be compared with the 3.68 micros orbit time of the Advanced Photon Source. The shutter provides high accuracy and efficient use of X-rays at a modest cost.

Charge Density Analysis of the (C−C)→Ti Agostic Interactions in a Titanacyclobutane Complex

The experimental electron density study of Ti(C(5)H(4)Me)(2)[(CH(2))(2)CMe(2)] provides direct evidence for the presence of (C-C)-->Ti agostic interactions. In accord with the model of Scherer and McGrady, the C(alpha)-C(beta) bond densities no longer show cylindrical symmetry in the vicinity of the Ti atom and differ markedly from those of the other C-C bonds. At the points along the C(alpha)-C(beta) bond where the deviation is maximal the electron density is elongated toward the metal center. The distortion is supported by parallel theoretical calculations. A calculation on an Mo complex in which the agostic interaction is absent supports the Scherer and McGrady criterion for agostic interactions. Despite the formal d(0) electron configuration for this Ti(IV) species, a significant nonzero population is observed for the d orbitals, the d orbital population is largest for the d(xy) orbital, the lobes of which point toward the two C(alpha) atoms. Of the three different basis sets for the Ti atom used in theoretical calculations with the B3LYP functional, only the 6-311++G** set for Ti agrees well with the experimental charge density distribution in the Ti-(C(alpha)-C(beta))(2) plane.

The RATIO method for time-resolved Laue crystallography

A RATIO method for analysis of intensity changes in time-resolved pump-probe Laue diffraction experiments is described. The method eliminates the need for scaling the data with a wavelength curve representing the spectral distribution of the source and removes the effect of possible anisotropic absorption. It does not require relative scaling of series of frames and removes errors due to all but very short term fluctuations in the synchrotron beam.

Static and time-resolved photocrystallographic studies in supramolecular solids

Abstract The supramolecular solid state is a medium par excellence for photochemical studies of molecules in a well-defined environment. If the photoactive molecule is embedded within a strong photochemically-inert framework, reactions can proceed without breakdown of the crystal lattice. A number of examples of trans-cis and cis-trans reactions are presented. A variable temperature study of Zn-coordinated tiglic acid shows that the reaction is energy-controlled with a small activation energy of approx. 2 kJ/mol, dependent on the size of the cavity in which the molecule is located. Time-resolved studies of the instantaneous dimer-formation of an organic and an inorganic species are presented. The Cu(I)(NH3)2 cation forms a dimeric species with a contracted Cu(I)—Cu(I) distance through promotion of an electron from an antibonding to a weakly bonding orbital, whereas xanthone forms an excimer with decrease interplanar spacing. The concept of the photodifference map is defined and used thoughout the article.

On the design of ultrafast shutters for time-resolved synchrotron experiments

A comprehensive treatment of the limitations and possibilities for single-pulse selection in synchrotron operating modes with approximately 150 ns bunch separation, as occurs in the standard operating mode at the Advanced Photon Source, is presented. It is shown that the strength of available materials and allowable kinetic energy build-up limit single-bunch selection for this separation to sample sizes of approximately 100 microm, and that for minimization of kinetic energy build-up it is preferable to increase the r.p.m. within physically acceptable limits rather than increase the disc radius to obtain a desirable peripheral speed. A slight modification of the equal-bunch spacing standard fill patterns is proposed that allows use of samples as large as 500 microm. The corresponding peripheral speed of the chopper wheel is approximately 600 m s(-1), which is within the limits of high-strength titanium alloys. For smaller samples, peripheral speeds are proportionally lower. Versatility can be achieved with interchangeable chopper wheels and the use of different orientations of the rotation axis relative to the X-ray beam, which opens the possibility of larger, rather than one-of-a-kind, production runs.

Thiocyanate-Ligated Heterobimetallic {PtM} Lantern Complexes Including a Ferromagnetically Coupled 1D Coordination Polymer

A series of heterobimetallic lantern complexes with the central unit {PtM(SAc)4(NCS)} have been prepared and thoroughly characterized. The {Na(15C5)}[PtM(SAc)4(NCS)] series, 1 (Co), 2 (Ni), 3 (Zn), are discrete compounds in the solid state, whereas the {Na(12C4)2)}[PtM(SAc)4(NCS)] series, 4 (Co), 5 (Ni), 6 (Zn), and 7 (Mn), are ion-separated species. Compound 7 is the first {PtMn} lantern of any bridging ligand (carboxylate, amide, etc.). Monomeric 1-7 have M(2+), necessitating counter cations that have been prepared as {(15C5)Na}(+) and {(12C4)2Na}(+) variants, none of which form extended structures. In contrast, neutral [PtCr(tba)4(NCS)]∞ 8 forms a coordination polymer of {PtCr}(+) units linked by (NCS)(-) in a zigzag chain. All eight compounds have been thoroughly characterized and analyzed in comparison to a previously reported family of compounds. Crystal structures are presented for compounds 1-6 and 8, and solution magnetic susceptibility measurements are presented for compounds 1, 2, 4, 5, and 7. Further structural analysis of dimerized {PtM} units reinforces the empirical observation that greater charge density along the Pt-M vector leads to more Pt···Pt interactions in the solid state. Four structural classes, one new, of {MPt}···{PtM} units are presented. Solid state magnetic characterization of 8 reveals a ferromagnetic interaction in the {PtCr(NCS)} chain between the Cr centers of J/kB = 1.7(4) K.

Supramolecular solids and time-resolved diffraction

Supramolecular solids are an ideal medium for time-resolved diffraction studies at atomic resolution as they allow dilution of the active species, and the study of a species in different states of aggregation and different environments, but attention must be paid to excited-state quenching due to energy transfer. Crystallinity must be preserved up to reasonable product concentrations if chemical reactions are to be monitored at the atomic level.

Competitive isomerization and dimerization in co-crystals of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol and sorbic acid: a new look at stereochemical requirements for [2+2] dimerization

Competitive [2+2] photodimerization and E-->Z isomerization reactions occur in a co-crystal of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol upon irradiation with 325 nm light. At 90 K both reactions are observed, whereas at 280 K the dimerization reaction is very fast and inhibits isomerization as the nature of the chromophore is affected by the reaction. The temperature dependence of the stereospecificity of the dimerization reaction is related to the large sliding motion required to bring the reacting molecules into juxtaposition. The progress of the reactions has been monitored by photocrystallographic methods.