@article{capracotta_sullivan_martin_2006, title={Sorptive reconstruction of CuMCl4 (M = Al and Ga) upon small-molecule binding and the competitive binding of CO and ethylene}, volume={128}, ISSN={["1520-5126"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-33750078396&partnerID=MN8TOARS}, DOI={10.1021/ja063172q}, abstractNote={Carbonyl adducts to CuMCl(4) (M = Al and Ga) have been characterized by single-crystal and/or powder X-ray diffraction, IR and diffuse reflectance UV/vis spectroscopy. Up to two equivalents of carbon monoxide ( approximately 200 cm(3)/g relative to stp) are sorbed at room temperature, with equilibrium binding pressures of below 0.5 atm of CO. The carbonyl bonding is shown to be nonclassical, implicating the dominance of sigma-bonding and absence of pi-back-bonding. Analysis of the crystalline structures of the parent and adduct phases provides an atomistic picture of the sorptive reconstruction reaction. Comparison of the reactivity of CO and ethylene with these CuMCl(4) materials, as well as other copper(I) halide compounds that exhibit classical and nonclassical modes of bonding, demonstrates the ability to tune the reactivity of the crystalline frameworks with selectivity for carbon monoxide or olefins, respectively.}, number={41}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Capracotta, Michael D. and Sullivan, Roger M. and Martin, James D.}, year={2006}, month={Oct}, pages={13463–13473} }
 @article{sullivan_liu_smith_hanson_osterhout_ciraolo_grey_martin_2003, title={Sorptive reconstruction of the CuAlCl4 framework upon reversible ethylene binding}, volume={125}, ISSN={["0002-7863"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0042233756&partnerID=MN8TOARS}, DOI={10.1021/ja036172o}, abstractNote={Three ethylene adducts to CuAlCl(4) have been characterized by single crystal and/or powder X-ray diffraction, (13)C, (27)Al and (63)Cu MAS NMR and diffuse reflectance UV-vis spectroscopy. (C(2)H(4))(2)CuAlCl(4), a = 7.1274(5) b = 12.509(1) c = 11.997(3) beta = 91.19 degrees, Pc, Z = 4; alpha-(C(2)H(4))CuAlCl(4), a =7.041(3) b = 10.754(8) c =11.742(9) beta = 102.48(6), P2(1), Z = 4 and beta-(C(2)H(4))CuAlCl(4), a = 7.306(2), b = 16.133(3), c = 7.094(1), Pna2(1), Z = 4. Up to 2 equiv of ethylene ( approximately 200 cm(3)/g relative to stp) are sorbed at room temperatures and pressures as low as 300 Torr. The ethylene ligands are bound to copper (I) primarily through a sigma-interaction, because the AlCl(4)(-) groups also bound to copper prevent any significant pi-back-bonding. The olefin binding is reversible and has been characterized by gravimetric and volumetric adsorption analysis and by time and pressure resolved synchrotron powder X-ray diffraction. Comparison of the parent crystal structure to those of the adduct phases provide an atomistic picture of the sorptive reconstruction reactions. These are proposed to proceed by a classic substitution mechanism that is directed by the van der Waals channels of the parent crystalline lattice.}, number={36}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Sullivan, RM and Liu, HM and Smith, DS and Hanson, JC and Osterhout, D and Ciraolo, M and Grey, CP and Martin, JD}, year={2003}, month={Sep}, pages={11065–11079} }
 @article{liu_sullivan_hanson_grey_martin_2001, title={Kinetics and mechanism of the beta- to alpha-CuAlCl4 phase transition: A time-resolved Cu-63 MAS NMR and powder X-ray diffraction study}, volume={123}, ISSN={["0002-7863"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0034802305&partnerID=MN8TOARS}, DOI={10.1021/ja010688v}, abstractNote={The beta and alpha phases of CuAlCl(4) have been characterized by solid-state (27)Al and (63)Cu magic angle spinning nuclear magnetic resonance. The very short spin--lattice relaxation times of the copper spins, and the sensitivity of the I = 3/2 (63)Cu nucleus to the small differences in the local structure of Cu in the two phases, allowed (63)Cu spectra to be acquired in very short time periods (1 min), in which the beta and alpha phases were clearly resolved. This time resolution was exploited to follow the phase transition from the pseudohexagonal close-packed beta-CuAlCl(4) into the pseudocubic close-packed alpha-CuAlCl(4), which occurs above 100 degrees C. In situ time-resolved (63)Cu MAS NMR and synchrotron X-ray diffraction experiments were used to measure the kinetics of this phase transition as a function of temperature. The transformation was shown to be a first-order phase transition involving no intermediate phases with an activation energy of 138 kJ/mol. The kinetic data obey a first-order Avrami--Erofe'ev rate law. A one-dimensional growth mechanism is proposed that involves a combination of Cu(+) ion self-diffusion and a translational reorganization of the close-packed anion layers imposed by the periodic rotations of [AlCl(4)](-) tetrahedra. This beta to alpha phase transformation can be induced at ambient temperatures by low partial pressures of ethylene.}, number={31}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Liu, HM and Sullivan, RM and Hanson, JC and Grey, CP and Martin, JD}, year={2001}, month={Aug}, pages={7564–7573} }
 @article{sullivan_martin_1999, title={An illuminating framework: Understanding the photoluminescence of alpha-CuAlCl4}, volume={121}, ISSN={["1520-5126"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0033520680&partnerID=MN8TOARS}, DOI={10.1021/ja9925204}, abstractNote={CuAlCl4 exemplifies a new class of phosphors based on metal halide analogues of aluminophosphates. The α- and β-CuAlCl4 phases show brilliant blue to blue-green luminescence. The electronic structure of the CuAlCl4 corner sharing tetrahedral frameworks has been explored by fluorimetric and diffuse reflectance measurements on the isomorphous series α-CuAlBrxCl4-x (x = 0−4). The photoluminescence is demonstrated to be a bulk property of the electronically isolated CuCl4/2 tetrahedra within the framework matrix. Remarkably, the structural framework is flexible such that at least 1 mol of small molecule gases per CuAlCl4 formula unit can be reversibly sorbed. The sorption/desorption of small molecule gases further results in the reversible quenching of the photoluminescence.}, number={43}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Sullivan, RM and Martin, JD}, year={1999}, month={Nov}, pages={10092–10097} }