Synthesis, characterization and photophysical study of a series of neutral isocyano rhodium(I) complexes with pyridylindolide ligands

Pyridylindole ligand and its chloro substituted derivatives have been synthesized and incorporated into the square planar bis(phenylisocyano) rhodium(I) complexes to give a series of neutral rhodium(I) complexes with general formula of [Rh( X-pyind)(CNR) 2] (R = 2,6-(CH 3) 2-4-BrC 6H 2, 2,4-Cl 2-6-(CH 3O)C 6H 2, 2,4,6-Br 3C 6H 2, 2,4,6-Cl 3C 6H 2 ; L = 2-(2′-pyridyl)indole, 5-chloro-2-(2′-pyridyl)indole, 4,6-dichloro-2-(2′-pyridyl)indole). The structures of two complex precursors [Rh(cod)( Cl-pyind)] and [Rh(cod)( Cl 2pyind )], and the target complex [Rh( pyind)(CNC 6H 2-2,4-Cl 2-6-(OCH 3)) 2] were determined by X-ray crystallography. The UV–vis absorption properties of these complexes and their responses towards the change of temperature were also investigated. A new class of neutral square planar bis(phenylisocyano) rhodium(I) complexes with pyridylindolide ligands with general formula of [Rh( X-pyind)(CNR) 2] has been synthesized. The UV–vis absorption and thermochromic properties of these complexes were also investigated

Aggregation and DNA intercalation properties of Di(isocyano) rhodium(I) Diimine complexes

A series of di(isocyano) rhodium(I) diimine complexes has been synthesized and characterized. Owing to the aggregation affinity of these complexes, they were found to exhibit thermochromism. To provide further insights into the aggregation affinity of these complexes, the enthalpy (δH) and entropy (δS) changes of dimerizations of some of the complexes have been determined. In addition, the DNA intercalation properties of these complexes have also been investigated by the DNA unwinding assay

Synthesis, Structures, and Photophysical Properties of Ruthenium(II) Quinolinolato Complexes

Reaction of [Ru^II(PR₃)₃Cl₂] with 2-methyl<b>-</b>8-quinolinolate (MeQ) in the presence of Et₃N in MeOH produced the neutral carbonyl hydrido complexes [Ru^II(MeQ)­(PR₃)₂(CO)­(H)] (R = Ph (<b>1</b>), MeC₆H₄ (<b>2</b>), MeOC₆H₄ (<b>3</b>)). An analogous reaction occurs between [Ru^II(PPh₃)₃Cl₂] and MeQH in ethanol to give [Ru^II(MeQ)­(PPh₃)₂(CO)­(CH₃)] (<b>4</b>). The carbonyl, hydride, and methyl ligands of these complexes are most likely derived from the decarbonylation of ROH. Reaction of [Ru^II(PPh₃)₃(CO)­(H)₂] with 5-substituted quinolinolato ligands (XQ, X = H, Cl, Ph) produced the neutral complexes [Ru^II(XQ)­(PPh₃)₂(CO)­(H)] (XQ = Q (<b>5</b>), ClQ (<b>6</b>), PhQ (<b>7</b>)). Treatment of <b>1</b> and <b>5</b>–<b>7</b> with excess KCN in MeOH following by metathesis with PPh₄Cl afforded PPh₄⁺ salts of the anionic carbonyl dicyano complexes [Ru^II(XQ)­(CO)­(CN)₂(PPh₃)]⁻ (XQ = MeQ (<b>8</b>), Q (<b>9</b>) ClQ (<b>10</b>), PhQ (<b>11</b>)). Under similar conditions, reaction of <b>1</b> with excess CyNC in the presence of NH₄PF₆ afforded [Ru^II(MeQ)­(CyNC)₂(CO)­(PPh₃)]⁺ (<b>12</b>). All complexes have been characterized by IR, ESI/MS, ¹H NMR and elemental analysis. The crystal structures of complexes <b>3</b>, <b>4</b>, <b>8</b>, and <b>12</b> have been determined by X-ray crystallography. The UV and emission spectra of these complexes have also been investigated. All complexes exhibit short-lived quinolinolate-based LC fluorescence in solution at room temperature and dual emissions derived from LC fluorescence and phosphorescence at 77 K glassy medium. These emissions are relatively insensitive to the nature of the ancillary ligands but are readily tunable by varying the substituents on the quinolinolato ligand

Synthesis, Structures, and Photophysical Properties of Ruthenium(II) Quinolinolato Complexes

Reaction of [Ru^II(PR₃)₃Cl₂] with 2-methyl<b>-</b>8-quinolinolate (MeQ) in the presence of Et₃N in MeOH produced the neutral carbonyl hydrido complexes [Ru^II(MeQ)­(PR₃)₂(CO)­(H)] (R = Ph (<b>1</b>), MeC₆H₄ (<b>2</b>), MeOC₆H₄ (<b>3</b>)). An analogous reaction occurs between [Ru^II(PPh₃)₃Cl₂] and MeQH in ethanol to give [Ru^II(MeQ)­(PPh₃)₂(CO)­(CH₃)] (<b>4</b>). The carbonyl, hydride, and methyl ligands of these complexes are most likely derived from the decarbonylation of ROH. Reaction of [Ru^II(PPh₃)₃(CO)­(H)₂] with 5-substituted quinolinolato ligands (XQ, X = H, Cl, Ph) produced the neutral complexes [Ru^II(XQ)­(PPh₃)₂(CO)­(H)] (XQ = Q (<b>5</b>), ClQ (<b>6</b>), PhQ (<b>7</b>)). Treatment of <b>1</b> and <b>5</b>–<b>7</b> with excess KCN in MeOH following by metathesis with PPh₄Cl afforded PPh₄⁺ salts of the anionic carbonyl dicyano complexes [Ru^II(XQ)­(CO)­(CN)₂(PPh₃)]⁻ (XQ = MeQ (<b>8</b>), Q (<b>9</b>) ClQ (<b>10</b>), PhQ (<b>11</b>)). Under similar conditions, reaction of <b>1</b> with excess CyNC in the presence of NH₄PF₆ afforded [Ru^II(MeQ)­(CyNC)₂(CO)­(PPh₃)]⁺ (<b>12</b>). All complexes have been characterized by IR, ESI/MS, ¹H NMR and elemental analysis. The crystal structures of complexes <b>3</b>, <b>4</b>, <b>8</b>, and <b>12</b> have been determined by X-ray crystallography. The UV and emission spectra of these complexes have also been investigated. All complexes exhibit short-lived quinolinolate-based LC fluorescence in solution at room temperature and dual emissions derived from LC fluorescence and phosphorescence at 77 K glassy medium. These emissions are relatively insensitive to the nature of the ancillary ligands but are readily tunable by varying the substituents on the quinolinolato ligand