Chiral S-1,1′-bi-2-naphthol (S-BINOL) as a synthon for supramolecular hydrogen-bonded {(S-BINOLATn-)(S-BINOL)n}-strands with naphthyl-paneled cavities or channels for a Cd(NH3)4 fragment (n=2) or [Ag(NH3)2]+ (n=1).: Part 2

The molecule 1,1'-bi-2-naphthol (BINOL) shows a propensity for supramolecular, hydrogen-bonded strand formation when crystallized with its deprotonated form BINOLAT(2-) or BINOLAT(-) (in conc. ammonia). The strand adapts from racemic rac-BINOL to enantiomeric S-BINOL and from di- to monocationic metal ions but keeps the overall strand feature. The structure of [Cd2+(S-BINOLAT(2-)-kappa O-2,O')(NH3)(4)](S-BINOL)(2)(H2O)(MeOH)(2) (1) can be correlated to the known structures of [M(NH3)(6)](2+)(rac-BINOLAT(2-))(rac-BINOL)(2)(M = Ni, Cd) despite the direct Cd-O,O'-BINOLAT chelate coordination in the former. With Ag+ as a monocationic metal structures of the formula [Ag(NH3)(2)](+)(S-BINOLAT(-))(S-BINOL)(EtOH) (2) and [Ag(NH3)(2)](+)(S-BINOLAT(-))(S-BINOL)(H2O)(2)(MeOH) (3) are formed from ethanol or methanol, respectively. Crystallization of Ag+/NH3 with rac-BINOL from EtOH also yields 2 with a spontaneous resolution to an enantiomeric excess of ca. 40%. Simultaneous differential thermoanalysis, thermogravimetry and mass spectrometry (DTA-TG-MS) show that the EtOH, MeOH and H2O solvent of crystallization together with the NH3 ligands can be removed before the BINOL moieties. X-Ray powder diffraction (XRPD) still shows the sample of 1 to be crystalline after the loss of solvent of crystallization. Upon heating to 130 degrees C the needle-shaped crystals of 2 keep their shape, yet darken ( formation of Ag by XRPD) and turn amorphous, with small crystal "prickles'' ( BINOL by XRPD) forming on the surface. The difference in metal coordination between 1 and [Cd(NH3)(6)](2+)(rac-BINOLAT(2-))(rac-BINOL)(2) is evidenced by a strong maximum at 591 nm in the emission spectrum of 1 which is absent in the emission spectra of both BINOL and [Cd(NH3)(6)](2+)(rac-BINOLAT(2-))(rac-BINOL)(2). This maximum is assigned to a metal-ligand transition due to the direct Cd-O, O'-BINOLAT chelate coordination in 1.