2 research outputs found
Synthesis, Structures, and Photophysical Properties of Ruthenium(II) Quinolinolato Complexes
Reaction of [Ru<sup>II</sup>(PR<sub>3</sub>)<sub>3</sub>Cl<sub>2</sub>] with 2-methyl<b>-</b>8-quinolinolate (MeQ)
in the
presence of Et<sub>3</sub>N in MeOH produced the neutral carbonyl
hydrido complexes [Ru<sup>II</sup>(MeQ)Â(PR<sub>3</sub>)<sub>2</sub>(CO)Â(H)] (R = Ph (<b>1</b>), MeC<sub>6</sub>H<sub>4</sub> (<b>2</b>), MeOC<sub>6</sub>H<sub>4</sub> (<b>3</b>)). An analogous
reaction occurs between [Ru<sup>II</sup>(PPh<sub>3</sub>)<sub>3</sub>Cl<sub>2</sub>] and MeQH in ethanol to give [Ru<sup>II</sup>(MeQ)Â(PPh<sub>3</sub>)<sub>2</sub>(CO)Â(CH<sub>3</sub>)] (<b>4</b>). The carbonyl,
hydride, and methyl ligands of these complexes are most likely derived
from the decarbonylation of ROH. Reaction of [Ru<sup>II</sup>(PPh<sub>3</sub>)<sub>3</sub>(CO)Â(H)<sub>2</sub>] with 5-substituted quinolinolato
ligands (XQ, X = H, Cl, Ph) produced the neutral complexes [Ru<sup>II</sup>(XQ)Â(PPh<sub>3</sub>)<sub>2</sub>(CO)Â(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 PPh<sub>4</sub>Cl afforded
PPh<sub>4</sub><sup>+</sup> salts of the anionic carbonyl dicyano
complexes [Ru<sup>II</sup>(XQ)Â(CO)Â(CN)<sub>2</sub>(PPh<sub>3</sub>)]<sup>−</sup> (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 NH<sub>4</sub>PF<sub>6</sub> afforded [Ru<sup>II</sup>(MeQ)Â(CyNC)<sub>2</sub>(CO)Â(PPh<sub>3</sub>)]<sup>+</sup> (<b>12</b>). All complexes
have been characterized by IR, ESI/MS, <sup>1</sup>H 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<sup>II</sup>(PR<sub>3</sub>)<sub>3</sub>Cl<sub>2</sub>] with 2-methyl<b>-</b>8-quinolinolate (MeQ)
in the
presence of Et<sub>3</sub>N in MeOH produced the neutral carbonyl
hydrido complexes [Ru<sup>II</sup>(MeQ)Â(PR<sub>3</sub>)<sub>2</sub>(CO)Â(H)] (R = Ph (<b>1</b>), MeC<sub>6</sub>H<sub>4</sub> (<b>2</b>), MeOC<sub>6</sub>H<sub>4</sub> (<b>3</b>)). An analogous
reaction occurs between [Ru<sup>II</sup>(PPh<sub>3</sub>)<sub>3</sub>Cl<sub>2</sub>] and MeQH in ethanol to give [Ru<sup>II</sup>(MeQ)Â(PPh<sub>3</sub>)<sub>2</sub>(CO)Â(CH<sub>3</sub>)] (<b>4</b>). The carbonyl,
hydride, and methyl ligands of these complexes are most likely derived
from the decarbonylation of ROH. Reaction of [Ru<sup>II</sup>(PPh<sub>3</sub>)<sub>3</sub>(CO)Â(H)<sub>2</sub>] with 5-substituted quinolinolato
ligands (XQ, X = H, Cl, Ph) produced the neutral complexes [Ru<sup>II</sup>(XQ)Â(PPh<sub>3</sub>)<sub>2</sub>(CO)Â(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 PPh<sub>4</sub>Cl afforded
PPh<sub>4</sub><sup>+</sup> salts of the anionic carbonyl dicyano
complexes [Ru<sup>II</sup>(XQ)Â(CO)Â(CN)<sub>2</sub>(PPh<sub>3</sub>)]<sup>−</sup> (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 NH<sub>4</sub>PF<sub>6</sub> afforded [Ru<sup>II</sup>(MeQ)Â(CyNC)<sub>2</sub>(CO)Â(PPh<sub>3</sub>)]<sup>+</sup> (<b>12</b>). All complexes
have been characterized by IR, ESI/MS, <sup>1</sup>H 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