Construction Of Coordination Networks Research Articles

Assembly of Layer-Type Organosilver(I) Complexes Incorporating Nitrate and Isomeric Halophenylethynide Ligands

Single-crystal X-ray analysis of a series of 10 silver(i) nitrate complexes containing carbon-rich ligands each composed of a halosubstituted phenyl nucleus bearing a terminal ethynyl group at various positions provided detailed information on the influence of ligand disposition and orientation, coordination preferences, and the co-existence of silver(i)–ethynide and silver(i)–halogen interactions in the construction of coordination networks, which are consolidated by argentophilic and weak intra or intermolecular interactions.

Systematic Investigation of Silver-Carbon Bonding in Coordination Frameworks with Aryl Ligands That Contain Ethynyl and Ethenyl Substituents

Single-crystal X-ray diffraction of a series of ten crystalline silver(I)-trifluoroacetate complexes that contained designed ligands, each of which was composed of an aromatic system that was functionalized with terminal and internal ethynyl groups and a vinyl substituent, provided detailed information on the influence of ligand disposition and orientation, coordination preferences, and the co-existence of different types of silver(I)-carbon bonding interactions (silver-ethynide, silver-ethynyl, silver-ethenyl, and silver-aromatic) on the construction of coordination networks that were consolidated by argentophilic and weak inter/intramolecular interactions. The complex AgL10⋅6 AgCF3CO2⋅H2O⋅ MeOH (HL10 = 1-{[4-(prop-2-ynyloxy)-3-vinylphenyl]ethynyl}naphthalene) is the first reported example that exhibits all four kinds of silver(I)-carbon bonding interactions in the solid state.

White Light Emission and Second Harmonic Generation from Secondary Group Participation (SGP) in a Coordination Network

We describe a white emitting coordination network solid that can be conveniently applied as a thin film onto a commercial UV-LED lamp for practical white lighting applications. The solid state material was discovered in an exercise of exploring molecular building blocks equipped with secondary groups for fine-tuning the structures and properties of coordination nets. Specifically, CH(3)SCH(2)CH(2)S- and (S)-CH(3)(OH)CHCH(2)S- (2-hydroxylpropyl) were each attached as secondary groups to the 2,5- positions of 1,4-benzenedicarboxylic acid (bdc), and the resultant molecules (L1 and L2, respectively) were crystallized with Pb(II) into the topologically similar 3D nets of PbL1 and PbL2, both consisting of interlinked Pb-carboxyl chains. While the CH(3)S- groups in PbL1 are not bonded to the Pb(II) centers, the hydroxy groups in PbL2 participate in coordinating to Pb(II) and thus modify the bonding features around the Pb(II), but only to a slight and subtle degree (e.g., Pb-O distances 2.941-3.116 Å). Interestingly, the subtle change in structure significantly impacts the properties, i.e., while the photoluminescence of PbL1 is yellowish green, PbL2 features bright white emission. Also, the homochiral side group in PbL2 imparts significant second harmonic generation, in spite of its seemingly weak association with the main framework (the NLO-phore). In a broad perspective, this work showcases the idea of secondary group participation (SGP) in the construction of coordination networks, an idea that parallels that of hemilabile ligands in organometallics and points to an effective strategy in developing advanced functions in solid state framework materials.

Controllable assembly of silver(I) complexes by variations of the carboxyl configuration: From a 2-D (45·6)2(418·610) layer to an unusual 3-D 5-connected self-penetrating (44·66)2 network

Abstract The reaction of AgClO4·6H2O with (+/−)-trans-epoxysuccinic acid (H2tes) in the presence of 2,6-dimethylpyridine afforded a three-dimensional (3-D) AgI coordination polymer [Ag2(tes)]∞ (1), which exhibits an unusual 5-connected self-penetrating (44·66)2 topological net (tes = (+/−)-trans-epoxysuccinate). Comparison of the structural differences with our relevant finding, a two-dimensional (2-D) (4,8)-connected (45·6)2(418·610) coordination polymer [Ag4(ces)2]∞ (S1) (ces = cis-epoxysuccinate), suggests that the carboxyl configuration on the ternary ring backbone of H2tes or H2ces ligand plays an important role in the construction of coordination networks.

Construction of coordination networks with high connectivity: a new 8-connected self-penetrating network based on tetranuclear metal clusters

Two highly connected cobalt(II) and zinc(II) coordination polymers with tetranuclear metal clusters as the nodes of network have been prepared, being the first example of an 8-connected self-penetrating net based on a cross-linked α-Po subnet.

Thioether ligands as molecular rods in silver(I) coordination networks: 1,4-dithiane as an analogue of pyrazine

The Ag(I) coordination networks, {[Ag(1,4-dithiane)]BF4}( and {[Ag2(1,4-dithiane)3](BF4)2}( have been prepared and structurally characterised, establishing the role of this simple thioether molecular rod in the construction of coordination networks. In the structure of {[Ag(1,4-dithiane)]BF4}( linear one-dimensional chains are formed, the arrangement of which is controlled by weak Ag⋯F2BF2 interactions [F⋯Ag = 2.886(2)Å]. In {[Ag2(1,4-dithiane)3]BF4)2}( an unusual honeycomb network is observed.