Interchain-solvent-induced chirality change of 1D helical chains: from achiral to chiral crystallization.
Three helical supramolecular stereoisomers of meso-2, Delta-2, and Delta-3 with the formula of cis-[Ni(f-rac-L)][Ni(CN)4] were successfully constructed based on the [Ni(f-rac-L)2+ and [Ni(CN)4]2- building blocks (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). In all three supramolecular stereoisomers, cis-[Ni(f-rac-L)]2+ cations are alternately bridged by [Ni(CN)4]2- anions through two cis (in meso-2 and Delta-2) or trans (in Delta-3) cyano groups to form one-dimensional (1D) helical chains of cis-[Ni(f-rac-L)][Ni(CN)4]. In meso-2, the right/left-handed chirality of the originally formed chain is transferred oppositely to adjacent chains through the interchain hydrogen-bonding interactions of hexameric water clusters, leading to the formation of meso-2 with a central symmetrical space group, P21/n, in which the 1D helical chains are packed in an alternating right- and left-handed chirality. In Delta-2 and Delta-3, the right/left-handed chirality of the original chain is transferred uniformly to adjacent chains through the zipper-like interchain hydrophobic interactions, resulting in the formation of Delta-2 and Delta-3 with chiral space groups of P212121 and P3121, respectively, in which all of the 1D helical chains are arranged in the same right/left-handed chirality.
Jiang
Long
L
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Instrumentation Analysis & Research Center, Sun Yat-Sen University, Guangzhou 510275, China.
Feng
Xiao-Long
XL
Su
Cheng-Yong
CY
Chen
Xiao-Ming
XM
Lu
Tong-Bu
TB
D002942:Circular Dichroism; D003460:Crystallization; D018360:Crystallography, X-Ray; D057927:Hydrophobic and Hydrophilic Interactions; D008958:Models, Molecular; D015394:Molecular Structure; D012997:Solvents / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
D012997:Solvents; D014867:Water