A new form of analytical chemistry: distinguishing the molecular structure of photo-induced states from ground-states.

This paper introduces a new analytical technique from the field of crystallography, and the optoelectronics motivation that underpins this effort. The essence of the photocrystallography technique is explained in the context of a four-dimensional (space-time) structural probe, and the four technically distinct time-windows of enquiry are presented. This features the complementary needs of laboratory, synchrotron and Free-electron laser based X-ray diffraction experiments. The different scales of atomic resolution required for the technique to be able to probe various photochemical phenomena are described. Sample requirements for photocrystallography experiments are also considered. The paper concludes by forecasting the prospective fortune of this new analytical technique to respond to major current challenges in the photovoltaic, optical data storage, and non-linear optics industries.

[1]  Lin X. Chen Taking snapshots of photoexcited molecules in disordered media by using pulsed synchrotron X-rays. , 2004, Angewandte Chemie.

[2]  Jacqueline M. Cole Applications of photocrystallography: a future perspective , 2008 .

[3]  Jacqueline M Cole,et al.  Single-crystal X-ray diffraction studies of photo-induced molecular species. , 2004, Chemical Society reviews.

[4]  S. Techert,et al.  Structure determination of the intramolecular charge transfer state in crystalline 4-(diisopropylamino)benzonitrile from picosecond X-ray diffraction. , 2004, Journal of the American Chemical Society.

[5]  M. W. George,et al.  Application of transient infrared and near infrared spectroscopy to transition metal complex excited states and intermediates , 2007 .

[6]  K. Moffat,et al.  Feasibility and Realization of Single-Pulse Laue Diffraction on Macromolecular Crystals at ESRF. , 1996, Journal of synchrotron radiation.

[7]  Philip Coppens,et al.  The first photocrystallographic evidence for light-induced metastable linkage isomers of ruthenium sulfur dioxide complexes. , 2002, Journal of the American Chemical Society.

[8]  W. Bainbridge,et al.  Societal implications of nanoscience and nanotechnology , 2001 .

[9]  Seth R. Marder,et al.  Molecular materials for second‐order nonlinear optical applications , 1993 .

[10]  Ahmed H. Zewail,et al.  4D Electron Microscopy: Imaging in Space and Time , 2009 .

[11]  B. Delley,et al.  [Ru(py)4Cl(NO)](PF6)2.0.5H2O: a model system for structural determination and ab initio calculations of photo-induced linkage NO isomers. , 2009, Acta crystallographica. Section B, Structural science.

[12]  Philip Coppens,et al.  Light-induced metastable linkage isomers of ruthenium sulfur dioxide complexes. , 2003, Inorganic chemistry.

[13]  J. Cole 'In-situ' charge-density studies of photoinduced phenomena: possibilities for the future? , 2004, Acta crystallographica. Section A, Foundations of crystallography.

[14]  Philip Coppens,et al.  A fast mechanical shutter for submicrosecond time-resolved synchrotron experiments. , 2005, Journal of synchrotron radiation.

[15]  Larry R Dalton,et al.  Electric field poled organic electro-optic materials: state of the art and future prospects. , 2010, Chemical reviews.

[16]  M. Grätzel,et al.  A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films , 1991, Nature.

[17]  S. Teat,et al.  A prototype chopper for synchrotron time-resolved crystallographic measurements. , 2010, The Review of scientific instruments.

[18]  P. Luksch,et al.  New developments in the Inorganic Crystal Structure Database (ICSD): accessibility in support of materials research and design. , 2002, Acta crystallographica. Section B, Structural science.

[19]  P. Coppens,et al.  On the Analysis of Reversible Light-Induced Changes in Molecular Crystals , 1998 .

[20]  T. Vogt,et al.  Ground- and light-induced metastable states of sodiumnitroprusside , 1992 .

[21]  F. Allen The Cambridge Structural Database: a quarter of a million crystal structures and rising. , 2002, Acta crystallographica. Section B, Structural science.

[22]  A. Parker,et al.  A Time-Resolved Infrared Vibrational Spectroscopic Study of the Photo-Dynamics of Crystalline Materials , 2009, Applied spectroscopy.

[23]  Andrew L. Johnson,et al.  Reversible 100% linkage isomerization in a single-crystal to single-crystal transformation: photocrystallographic identification of the metastable [Ni(dppe)(eta1-ONO)Cl] isomer. , 2009, Angewandte Chemie.

[24]  P. Coppens,et al.  On the design of ultrafast shutters for time-resolved synchrotron experiments. , 2007, Journal of synchrotron radiation.

[25]  P. Liska,et al.  Acid-Base Equilibria of (2,2'-Bipyridyl-4,4'-dicarboxylic acid)ruthenium(II) Complexes and the Effect of Protonation on Charge-Transfer Sensitization of Nanocrystalline Titania. , 1999, Inorganic chemistry.

[26]  M. Carducci,et al.  Diffraction Studies of Photoexcited Crystals: Metastable Nitrosyl-Linkage Isomers of Sodium Nitroprusside , 1997 .