Novel complexes constructed by flexible 1,2,3,4,5,6- cyclohexanehexacarboxylate and transition metal ions – From 0D mononuclear to 3D porous coordination polymers

• Published in: CrystEngComm Vol. 14; no. 13; pp. 4312 - 4322
• Main Authors: Xing, Feifei, Bai, Yueling, He, Xiang, Jia, Juan, Zhou, Dong, Shao, Min, Zhu, Shourong
• Format: Journal Article
• Language: English
• Published: 01.01.2012
• Subjects: Carboxylates; Coordination numbers; Coordination polymers; Cyclohexane; Least squares method; Networks; Three dimensional; Transition metals
• ISSN: 1466-8033; 1466-8033
• DOI: 10.1039/c2ce25283j

Nine novel coordination polymers were prepared from flexible 1,2,3,4,5,6-cyclohexanehexacarboxylate (H sub(6)L) and corresponding metal ions at room temperature and/or hydrothermal conditions, namely from binary {[Zn sub(3)( eta sub(9)-L super(I))( eta sub(2)-H sub(2)O) sub(1)( eta sub(1)-H sub(2)O) sub( 7)]. (H sub(2)O) sub(5)} super(3) sub(n) (1), {[Co sub(3)( eta sub(9)-L super(I))( eta sub(2)-H sub(2)O) sub(1)( eta sub(1)-H sub(2)O) sub( 7)]. (H sub(2)O) sub(5)} super(3) sub(n) (2), {[Cu sub(5)( eta sub(8)-HL super(I)) sub(2).10H sub(2)O].(H sub(2)O) sub(4)} super(3) sub() n(3), {[Ni sub(3)( eta sub(12)-L super(II))( eta sub(1)-H sub(2)O) sub(6)].1.5H sub( 2)O} super(3) sub(n) (4), to ternary {[Zn( eta sub(3)-H sub(4)L super(I))(4,4'-bipy)( eta sub(1)-H sub(2)O)].(H sub(2)O)d2 super(2) sub(n) (5), {[Zn sub(2)( eta sub(4)-H sub(3)L super(I))(1,10-phen) sub(3).( eta sub(1)-NO sub(3))]. H sub(2)O} super(1 ) sub(n) (6), {[Cd sub(2)( eta sub(4)-H sub(4)L super(I)) sub(2)(2,2'-bipy) sub(2)( eta sub( 1)-H sub(2)O) sub(2)].(2,2'-bipy).(H sub(2)O) sub(3)} super(1) sub(n) (7), {[Co sub(1.5)( eta sub(3)-H sub(3)L super(I))( eta sub(1)-4,4'-bipy) sub(3)( eta sub(1)-H sub(2)O) sub(3)].6H sub(2)O} super(1) sub(n) (8), [Mn(1,10-phen) sub(2)(H sub(2)O) sub(2)].(H sub(4)L super(I)).(H sub(2)O) sub(5 ) (9) (L super(I) = all-cis(a,e,a,e,a,e) conformation L super(6-), L super(II) = all-trans(e,e,e,e,e,e) conformation L super(6-), where aand erepresent the carboxylate that is almost perpendicular/parallel to the least square of the cyclohexane moiety. 2,2'-bpy = 2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine, 1,10-phen = 1,10-phenanthroline). Complexes 1, 2, 3 and 4 have 3D coordination frameworks, in which H sub(6)L are fully deprotonated or only mono-protonated, their coordination numbers are 8, 9 and 12. Complexes 1 and 2 are isomorphous with each other and exhibit 3,5-connected with {3 super(2); 4}{3; 6 super(3); 8 super(6)} network in the Schlafli notation. Complex 3 is a 3,6-connected {4 super(3)}{4 super(5); 6 super(7); 8 super(3)} network. Complex 4 is a 3,9-connected 9-noted with {4 super(2); 6} sub(3){4 super(6); 6 super(21); 8 super(9)} network. 5-8 are ternary complexes with secondary building blocks where L binds 2 to 4 protons, respectively. The coordination number of L decreased to 3-4 in complexes 5-8. Complex 9 is a mononuclear complex where H sub(4)L super(2-) acts as a counter ion to balance the charge of the metal ion. The ligand in hydrothermal synthesized 4 adopts the all-transconfiguration L super(II), while in all the other room temperature complexes, L adopts an L super(I) configuration. As a role, it is always the e-position carboxylate that prefers to coordinate to the metal ion. The solid state photoluminescence studied indicates that there are ligand-centered emissions in 1, 5, 6, and 7. Complex 2 is a breathable porous coordination polymer, X-ray...