Abstract
Accompanied by a change in color from red to black, the enantiomorphic phases of the cobalt complexes of a chiral salen ligand (L2−, Co(L)·CS2, and Co(L) (L = LS,S or LR,R)) chemisorb NO (g) at atmospheric pressure and rt over hours for the CS2 solvated phase, and within seconds for the desolvated phase. NO is installed as an axial nitrosyl ligand. Aligned but unconnected voids in the CS2 desorbed Co(LR,R)·CS2 structure indicate conduits for the directional desorption of CS2 and reversible sorption of NO, which occur without loss of crystallinity. Vibrational circular dichroism (VCD) spectra have been recorded for both hands of LH2, Zn(L), Co(L)·CS2, Co(L), Co(NO)(L), and Co(NO)(L)·CS2, revealing significant differences between the solution-state and solid-state spectra. Chiral induction enables the detection of the νNO band in both condensed states, and surprisingly also the achiral lattice solvent (CS2 (νCS at 1514 cm−1)) in the solid-state VCD. Solution-state spectra of the paramagnetic Co(II) complex shows a nearly 10-fold enhancement and more extensive inversion of polarity of the vibrations of dominant VCD bands compared to the spectra of the diamagnetic compounds. This enhancement is less pronounced when there are fewer polarity inversions in the solid state VCD spectra.
Highlights
NO is biologically important, and a highly toxic gas, and materials for its sorptive removal from exhausts are of great interest
Vibrational circular dichroism (VCD) spectra have been recorded for both hands of LH2, Zn(L), Co(L)·CS2, Co(L), Co(NO)(L), and Co(NO)(L)·CS2, revealing significant differences between the solution-state and solid-state spectra
The crystals used for Single Crystal X-ray Diffraction (SCXRD) were taken directly from the mother liquor and mounted using Fomblin®Y to adhere the crystal to the mounting loop
Summary
NO is biologically important, and a highly toxic gas, and materials for its sorptive removal from exhausts are of great interest. Assuurrvveeyyooff tthhee Cambridge ssttrruuccttuurraallddaatatabbaassee[1[133] ]ofotfhtehecrcyrsytastlasltrsutrcutuctruesreosf omfemtaeltcaolmcopmlepxleesxoefsLo2f− sLu2g−gsuesgtgsetshtastththaet tpheerippehreiprahlebrualkbyultkeryt-tbeurtt-yblugtryolugprosuopf sLo2−feLn2s−uerensthuaret mthoant omnouncolenaurcCleoarsiCteos asirteesisaorleatiesodlafrtoedmfreoamcheoatchherotbhyerpbreyvpernetvinegnttihneg ftohremfoartmionatioofncroyfsctraylsptahlapsehsasceosnctaoinntianingidngimdiemriecri(cM(M(sa(sleanle)n)2))[214[1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41–81],8w], hwichhichfofromrmwwhehnenaapphhenenoolaltaotoooxxyyggeennaattoommooff eeaacchh salen on adjacent complexes bridge between the two metal ions Another advantage is that, unlike some phases of the parent Co(salen) and its derivativees, CCoo((LL)) does not bind O2. Peotewrduesriendg CsaumKpαlersadwieartieoand(hλer=e1d.5t4o1t8h4eÅm)oaunndtitnhgelCoorypsuAsliinsgPFRoOm1b.1li7n1®.4Y0, .a6n7da sduififtrea[c1t9o]g.rPaomwsdwereerde sreacmoprdleesdwweirtehaaddheetreecdtotro dthisetamnoceunotfin12g0lomomp ,uusisninggFGomanbdlionl®fiYs,caannds dwifitfhraactsoignrgalme skawpeprae setting, and an exposure time of 200 s
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