C. J. Brown

Bio: C. J. Brown is an academic researcher. The author has contributed to research in topics: Crystal structure & Azobenzene. The author has an hindex of 1, co-authored 1 publications receiving 261 citations.

Photoisomerization in different classes of azobenzene

Abstract: Azobenzene undergoes trans → cisisomerization when irradiated with light tuned to an appropriate wavelength. The reverse cis →transisomerization can be driven by light or occurs thermally in the dark. Azobenzene's photochromatic properties make it an ideal component of numerous molecular devices and functional materials. Despite the abundance of application-driven research, azobenzene photochemistry and the isomerization mechanism remain topics of investigation. Additional substituents on the azobenzene ring system change the spectroscopic properties and isomerization mechanism. This critical review details the studies completed to date on the 3 main classes of azobenzene derivatives. Understanding the differences in photochemistry, which originate from substitution, is imperative in exploiting azobenzene in the desired applications.

Dinitrogen Coordination Chemistry: On the Biomimetic Borderlands

Abstract: Biological nitrogen fixation by the nitrogenase enzymes has long been a touchstone for dinitrogen chemists.1,2 Both the enzymatic reduction and protonation of N2 mediated by these metalloenzymes (eq 1)3,4 and the industrial hydrogenation of N2 exemplified by the Haber-Bosch process (eq 2)5-7 employ transition metal-based catalysts to accelerate the thermodynamically feasible production of ammonia.

Novel photo-switching using azobenzene functional materials

Abstract: Azobenzene (azo) chromophores have been incorporated into a wide variety of materials and molecular architectures, including polymers, dendrimers, and molecular glasses. Azobenzene exhibits a uniquely clean and efficient photochemistry, with facile geometric isomerization about the azo bond, converting the molecule from trans to cis . This review discusses the extensive number of investigations of azobenzene photo-switching and photo-modulation. In particular, azos can be used to alter material behaviour with light, switching both molecular and macroscopic properties. A large number of photobiological studies have shown that interfacing the azo chromophore with enzymes and biopolymers is feasible and useful. The all-optical surface patterning unique to azobenzenes is also reviewed. Lastly, azobenzene photomechanical effects are discussed.

On the Mechanism of the cis−trans Isomerization in the Lowest Electronic States of Azobenzene: S0, S1, and T1

Abstract: In this paper, we identify the most efficient decay and isomerization route of the S1, T1, and S0 states of azobenzene. By use of quantum chemical methods, we have searched for the transition states (TS) on the S1 potential energy surface and for the S0/S1 conical intersections (CIs) that are closer to the minimum energy path on the S1. We found only one TS, at 60° of CNNC torsion from the E isomer, which requires an activation energy of only 2 kcal/mol. The lowest energy CIs, lying also 2 kcal/mol above the S1 minimum, were found on the torsion pathway for CNNC angles in the range 95−90°. The lowest CI along the inversion path was found ca. 25 kcal/mol higher than the S1 minimum and was characterized by a highly asymmetric molecular structure with one NNC angle of 174°. These results indicate that the S1 state decay involves mainly the torsion route and that the inversion mechanism may play a role only if the molecule is excited with an excess energy of at least 25 kcal/mol with respect to the S1 minimum...

Azobenzene photomechanics: prospects and potential applications

Abstract: The change in shape inducible in some photo-reversible molecules using light can effect powerful changes to a variety of properties of a host material. This class of reversible light-switchable molecules includes molecules that photo-dimerize, such as coumarins and anthracenes; those that allow intra-molecular photo-induced bond formation, such as fulgides, spiro-pyrans, and diarylethenes; and those that exhibit photo-isomerization, such as stilbenes, crowded alkenes, and azobenzenes. The most ubiquitous natural molecule for reversible shape change, however, and perhaps the inspiration for all artificial bio-mimics, is the rhodopsin/retinal protein system that enables vision, and this is the quintessential reversible photo-switch for performance and robustness. Here, the small retinal molecule embedded in a cage of rhodopsin helices isomerizes from a cis geometry to a trans geometry around a C=C double bond with the absorption of just a single photon. The modest shape change of just a few angstroms is quickly amplified and sets off a cascade of larger shape and chemical changes, eventually culminating in an electrical signal to the brain of a vision event, the energy of the input photon amplified many thousands of times in the process. Complicated biochemical pathways then revert the trans isomer back to cis, and set the system back up for another cascade upon subsequent absorption. The reversibility is complete, and many subsequent cycles are possible. The reversion mechanism back to the initial cis state is complex and enzymatic, hence direct application of the retinal/rhodopsin photo-switch to engineering systems is difficult. Perhaps the best artificial mimic of this strong photo-switching effect however in terms of reversibility, speed, and simplicity of incorporation, is azobenzene. Trans and cis states can be switched in microseconds with low-power light, reversibility of 105 and 106 cycles is routine before chemical fatigue, and a wide variety of molecular architectures is available to the synthetic materials chemist, permitting facile anchoring and compatibility, as well as chemical and physical amplification of the simple geometric change. This review article focuses on photo-mechanical effect taking place in various material systems incorporating azobenzene. The photo-mechanical effect can be defined as reversible change in shape by absorption of light, which results in a significant macroscopic mechanical deformation, and reversible mechanical actuation, of the host material. Thus, we exclude simple thermal expansion effects, reversible but non-mechanical photo-switching or photo-chemistry, as well as the wide range of optical and electro-optical switching effects for which good reviews exist elsewhere. Azobenzene-based material systems are also of great interest for light energy harvesting applications across much of the solar spectrum, yet this emerging field is still in an early enough stage of research output as to not yet warrant review, but we hope that some of the ideas put forward here toward promising future directions of research, will help guide the field.