TY - JOUR
T1 - A redox-active two-dimensional coordination polymer
T2 - Preparation of silver and gold nanoparticles and crystal dynamics on guest removal
AU - Suh, Myunghyun Paik
AU - Moon, Hoi Ri
AU - Lee, Eun Young
AU - Jang, Seung Yeon
PY - 2006/4/12
Y1 - 2006/4/12
N2 - A two-dimensional (2D) square-grid coordination polymer, {[Ni(cyclam)] 2[BPTC]}n·2nH2O (1), has been assembled from [Ni(cyclam)](ClO4)2 (cyclam = 1,4,8,11- tetraazacyclotetradecane) and H4BPTC (H4BPTC = 1,1′-biphenyl-2,2′,6,6′-tetracarboxylic acid) in H 2O/MeOH (2.5:1, v/v) in the presence of triethylamine. When solid 1 was immersed in the EtOH solutions of AgNO3 (1-3 × 10 -1 M) and NaAuCl42H2O (3.4 × 10 -2 M), respectively, for 5 min at room temperature, solids including Ag (3.7 ± 0.4 nm, diameter) and Au (2 nm, diameter) nanoparticles were formed by the redox reactions between Ni(II) ions incorporated in 1 and metal ions, as evidenced by HRTEM images, EPR, and XPS spectra. When single-crystal 1 was heated at 180 °C under 10-5 Torr for 24 h, it was transformed to dehydrated compound {[Ni(cyclam)]2[BPTC]}n (2) in the single-crystal-to-single-crystal manner. The X-ray crystal structure of 2 reveals extensive dynamic motions of the molecular components in response to guest removal, involving rotation of the carboxylate and macrocycle, swing of the biphenyl, and bending of the macrocyclic coordination plane toward the carboxylate plane, which reduces the interlayer distance.
AB - A two-dimensional (2D) square-grid coordination polymer, {[Ni(cyclam)] 2[BPTC]}n·2nH2O (1), has been assembled from [Ni(cyclam)](ClO4)2 (cyclam = 1,4,8,11- tetraazacyclotetradecane) and H4BPTC (H4BPTC = 1,1′-biphenyl-2,2′,6,6′-tetracarboxylic acid) in H 2O/MeOH (2.5:1, v/v) in the presence of triethylamine. When solid 1 was immersed in the EtOH solutions of AgNO3 (1-3 × 10 -1 M) and NaAuCl42H2O (3.4 × 10 -2 M), respectively, for 5 min at room temperature, solids including Ag (3.7 ± 0.4 nm, diameter) and Au (2 nm, diameter) nanoparticles were formed by the redox reactions between Ni(II) ions incorporated in 1 and metal ions, as evidenced by HRTEM images, EPR, and XPS spectra. When single-crystal 1 was heated at 180 °C under 10-5 Torr for 24 h, it was transformed to dehydrated compound {[Ni(cyclam)]2[BPTC]}n (2) in the single-crystal-to-single-crystal manner. The X-ray crystal structure of 2 reveals extensive dynamic motions of the molecular components in response to guest removal, involving rotation of the carboxylate and macrocycle, swing of the biphenyl, and bending of the macrocyclic coordination plane toward the carboxylate plane, which reduces the interlayer distance.
UR - http://www.scopus.com/inward/record.url?scp=33646062897&partnerID=8YFLogxK
U2 - 10.1021/ja056963l
DO - 10.1021/ja056963l
M3 - Article
AN - SCOPUS:33646062897
SN - 0002-7863
VL - 128
SP - 4710
EP - 4718
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 14
ER -