Neutral Cu4N12 and Ag4N12 metallacycles with a para-cyclophane framework assembled from copper(i) and silver(i) pyrazolates and pyridazine

Dias, H. V. Rasika; Diyabalanage, Himashinie V. K.; Gamage, Chammi S. Palehepitiya

doi:10.1039/b418306a

Cited by 46 publications

(13 citation statements)

References 20 publications

(13 reference statements)

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“…To date, the greatest bending of 1,b y3 8 8,w as reported for the Y-shaped complex with benzo[c]cinnoline, in which two coppera toms of the macrocycle coordinate to two nitrogen atoms of the aromatic molecule. [12] Geometry optimization of the complex [Cp*Fe(h 5 -P 5 )]·[(CuL) 3 ] (at BP86-D3/TZ2Pa nd PBEsol-D3-BJ/TZPl evels;s ee the Supporting Information for details) reveals the local minimum that reproduces all fundamental features of the X-ray structurefolding of the macrocycle and interaction of two Cu atoms with four phosphorus atoms. Fragment-based energy decompositiona nalysis with ADF2014( Ziegler-Rauk method) [13] gave af undamental pattern, which explains the observed high complex stability.…”

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confidence: 98%

Remarkable Structural and Electronic Features of the Complex Formed by Trimeric Copper Pyrazolate with Pentaphosphaferrocene

Filippov

Titov

Guseva

et al. 2015

Chemistry A European J

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According to spectroscopic (NMR, IR, UV/Vis) study, the interaction of pentaphosphaferrocene [Cp*Fe(η(5) -P5 )] with trimeric copper pyrazolate [(Cu{3,5-(CF3 )2 Pz})3 ] yields a new compound that is astonishingly stable in solution. Single-crystal X-ray analysis reveals unprecedented structural changes in the interacting molecules and the unique type of coordination [Cp*Fe(μ3 -η(5) :η(2) ,η(2) -P5 ){Cu(3,5-(CF3 )2 Pz)}3 ]. As a result of the 90° macrocycle folding, the copper atoms are able to behave both as a Lewis acid and as a Lewis base in the interaction with the cyclo-P5 ligand.

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confidence: 98%

Remarkable Structural and Electronic Features of the Complex Formed by Trimeric Copper Pyrazolate with Pentaphosphaferrocene

Filippov

Titov

Guseva

et al. 2015

Chemistry A European J

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“…In addition, these complexes showed the dramatic sensitivities to solvent, concentration, and excitation wavelengths in solid and solution states. (79a) and benzo[c]cinnoline (L66) at the molar ratio of 1:1 (Scheme 27) [187]. X-ray crystallographic data of 81 showed that the benzo[c]cinnoline was coordinated to two of the three copper atoms of 79a.…”

Section: Trinuclear Metallacyclesmentioning

confidence: 99%

“…UV-vis spectroscopy results The assembly of neutral metal-nitrogen based metallacycles with a cyclophane framework using copper(I) and silver(I) has been achieved [187]. Treatment of copper(I) pyrazolate 79a or silver(I) pyrazolate 79b with the pyridazine (L110) afforded [{3,5-(CF 3 ) 2 Pz} 4 M 4 (L110) 2 ] (M = Cu, 132a; Ag, 132b) in good yield.…”

Section: Scheme 40mentioning

confidence: 99%

“…Crystal structure of (a) 132a and (b) 132b[187]. complete hydrolysis of the HPNP substrate in less than 40 min under identical conditions.…”

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confidence: 99%

“…X-ray crystal structures of 80a-d showing the labeling scheme of a molecular unit (left) and the packing of the Cu3N6 metallacycles (right)[186].Scheme 27.Preparation of Cu-based metallacycle 81[187].…”

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Neutral discrete metal–organic cyclic architectures: Opportunities for structural features and properties in confined spaces

Thanasekaran

Lee

2014

Coordination Chemistry Reviews

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Homo‐ and Heteropolynuclear Platinum Complexes Stabilized by Dimethylpyrazolato and Alkynyl Bridging Ligands: Synthesis, Structures, and Luminescence

Forniés

Fuertes

Martín

et al. 2006

Chemistry A European J

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This work describes the synthesis of cis-[Pt(C[triple bond]CPh)2(Hdmpz)2] (1) and its use as a precursor for the preparation of homo- and heteropolynuclear complexes. Double deprotonation of compound 1 with readily available M(I) (M = Cu, Ag, Au) or M(II) (M = Pd, Pt) species affords the discrete hexanuclear clusters [{PtM2(mu-C[triple bond]CPh)2(mu-dmpz)(2)}(2)] [M = Cu (2), Ag (3), Au (4)], in which both "Pt(C[triple bond]CPh)2(dmpz)(2)" fragments are connected by four d(10) metal centers, and are stabilized by alkynyl and dimethylpyrazolate bridging ligands, or the trinuclear complexes [Pt(mu-C[triple bond]CPh)2(mu-dmpz)(2){M(C/\P)}2] (M = Pd (5), Pt (6); C/\P = CH(2)-C(6)H(4)-P(o-tolyl)2-kappaC,P), respectively. The X-ray structures of complexes 1-4 and 6 are reported. The X-ray structure of the platinum-copper derivative 2 shows that all copper centers exhibit similar local geometry being linearly coordinated to a nitrogen atom and eta(2) to one alkynyl fragment. However in the related platinum-silver (3) and platinum-gold (4) derivatives the silver and gold atoms present three different coordination environments. The complexes have been studied by absorption and emission spectroscopy. The hexanuclear complexes exhibit bright luminescence in the solid state and in fluid solution (except 4 in the solid state at 298 K). Dual long-lived emission is observed, being clearly resolved in low-temperature rigid media. The low-energy emission is ascribed to MLM'CT Pt(d)/pi(C[triple bond]CPh)-->Pt(p(z))/M'(sp)/pi*(C[triple bond]CPh) modified by metal-metal interactions whereas the high-energy emission is tentatively attributed to an emissive state derived from dimethylpyrazolate-to-metal (d(10)) LM'CT transitions pi(dmpz)-->M'(d(10)).

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Neutral Cu4N12 and Ag4N12 metallacycles with a para-cyclophane framework assembled from copper(i) and silver(i) pyrazolates and pyridazine

Cited by 46 publications

References 20 publications

Remarkable Structural and Electronic Features of the Complex Formed by Trimeric Copper Pyrazolate with Pentaphosphaferrocene

Remarkable Structural and Electronic Features of the Complex Formed by Trimeric Copper Pyrazolate with Pentaphosphaferrocene

Neutral discrete metal–organic cyclic architectures: Opportunities for structural features and properties in confined spaces

Homo‐ and Heteropolynuclear Platinum Complexes Stabilized by Dimethylpyrazolato and Alkynyl Bridging Ligands: Synthesis, Structures, and Luminescence

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