Structural and Nonlinear Optical Properties of Aligned Heterotrinuclear [Ru^II‐(Spacer)‐M^II‐(Spacer)‐Ru^II] Complexes (M=Pd, Pt; spacer=4‐ethynylpyridine)

Abstract

Lewis addition between the metalloligand [RuCp(C[triple bond]Cpy-4)(dppf)] (1) (dppf = (C(5)H(4)PPh(2))(2)Fe) and MCl(2)(CH(3)CN)(2) gives [RuCp(C[triple bond]Cpy-4)(dppf)](2)[MCl(2)] (M = Pd (2) and Pt (3)), all of which have been spectroscopically and crystallographically characterized. The mixed-metal adducts show the d(6)-d(8)-d(6) metal alignment maintained by the trans disposition of the directionally rigid 4-ethynylpyridine at the centrosymmetric square-planar metal center. Electrochemical studies of these and the related known complexes trans-[RuCl(C[triple bond]Cpy-4)(dppm)(2)] (4) and [trans-RuCl(C[triple bond]Cpy-4)(dppm)(2)](2)[MCl(2)] (dppm = Ph(2)PCH(2)PPh(2)) (M = Pd (5) and Pt (6)) suggest that the spacer-linked heterotrinuclear network is able to stabilize the oxidized Ru(III) better than the metalloligand precursor. Cubic nonlinear optical responses are also generally higher for the heterometallic complexes. The gamma(real) value of the PdRu(2) dppm complex 5 is among the largest for linear organometallic complexes.

Spacer directed metallo-supramolecular assemblies of pyridine carboxylates

“…A distinct feature of pyridinecarboxylates is their amenity for metalloligand construction [12,37,39,45,[90][91][92]. This is achieved by using metal substrates with limited coordination unsaturation so that only one of the two donor functions is engaged.…”

Organobimetallic RuII–ReI 4-ethynylpyridyl complexes: structures and non-linear optical properties

“…A mixture of [ReBr(CO) 5 ] (812 mg, 2.0 mmol) and tpy (466 mg, 2.0 mmol) in toluene (50 mL) was heated to reflux for 4 h. The solvent was removed under vacuum and the resultant residue washed 3 times with Et 2 O to afford 3 as a bright yellow solid with yield > 95% (> 1.1 g). 1 H-NMR: (300 MHz, CDCl 3 , 25 13 C-NMR: (300 MHz, CDCl 3 , 25…”

“…We have recently extended this to the assembly of symmetrical Ru-Pt-Ru heterotrimetallic pyridylacetylides. 12, 13 In this paper, we turn to the synthesis of the Ru(II)-Re(I) binuclear complexes from the half-sandwich [RuCp(C≡Cpy-4)(P-P)] (P-P = dppf 1; 2PPh 3 2) precursors, and report their structural and nonlinear optical activities. The possibility of similar materials being used in non-linear optics has been mooted 9 but has not been demonstrated to date.…”

Optimised Syntheses of the Half-Sandwich Complexes FeCl(dppe)Cp*, FeCl(dppe)Cp, RuCl(dppe)Cp*, and RuCl(dppe)Cp

“…[20,21] The ligand substitution chemistry that has been developed on various half-sandwich complexes has led to their use as building blocks in supramolecular architectures [22][23][24][25] and surface supported nanoarchitectures, [26,27] and as frameworks for the investigation of non-linear optical properties. [28][29][30][31][32][33] The synthetic versatility is augmented by well-defined one-electron redox processes [34,35] which opens a range of further possibilities for use of these systems as platforms through which to generate and study mixed-valence complexes and electron-transfer phenomena. [36][37][38][39][40] The ability to systematically vary the nature of the metal and the steric and electronic properties of the half-sandwich fragment has allowed detailed investigation of the electronic and spectroscopic properties of such complexes.…”