RuCp* Complexes of Ambidentate 4,5-Diazafluorene Derivatives: From Linkage Isomers to Coordination-Driven Self-Assembly

The coordination chemistry of the {RuCp*}⁺ fragment was studied toward several 4,5-diazafluorene derivatives. The ambidentate nature of these 4,5-diazafluorene derivatives with multiple coordination sites allowed for the syntheses of different linkage isomers and self-assembled macrocycles. Both a tetramer (<b>2</b>) and a monomer (<b>3</b>) of [RuCp*<b>L</b>] (where <b>L</b>^<b>–</b> = 4,5-diazafluorenide) were prepared with the <b>L</b>^<b>–</b> ligand. The dimeric head-to-tail macrocycles [Cp*Ru­(L_pH)]₂Cl₂ (<b>4</b>) and [Cp*RuL_p]₂ (<b>5</b>) were obtained with the ditopic <b>L</b>_<b>p</b><b>H</b> and <b>L</b>_<b>p</b>^<b>–</b> ligands (where <b>L</b>_<b>p</b><b>H</b> = 9-(2-(diphenylphosphino)­ethyl)-4,5-diazafluorene and <b>L</b>_<b>p</b>^<b>–</b> = 9-(2-(diphenylphosphino)­ethyl)-4,5-diazafluorenide). The bulky arene-substituted <b>L</b>_<b>Mes</b><b>H</b> ligand (where <b>L</b>_<b>Mes</b><b>H</b> = 3,6-dimesityl-4,5-diazafluorene) was prepared, and its coordination to {RuCp*}⁺ gave [Cp*Ru­(<b>L</b>_<b>Mes</b><b>H</b>)]Cl (<b>13</b>). The selective syntheses of different linkage isomers of [RuCp*­(<b>L</b>_<b>Mes</b>)] (<b>14</b> and <b>15</b>) (where <b>L</b>_<b>Mes</b>^<b>–</b> = 3,6-dimesityl-4,5-diazafluorenide) were also demonstrated

Percentage distribution by the Fuhrman grade.

<p>Percentage distribution by the Fuhrman grade.</p

Average size of tumor prediction.

<p>Average size of tumor prediction.</p

RuCp* Complexes of Ambidentate 4,5-Diazafluorene Derivatives: From Linkage Isomers to Coordination-Driven Self-Assembly

The coordination chemistry of the {RuCp*}⁺ fragment was studied toward several 4,5-diazafluorene derivatives. The ambidentate nature of these 4,5-diazafluorene derivatives with multiple coordination sites allowed for the syntheses of different linkage isomers and self-assembled macrocycles. Both a tetramer (<b>2</b>) and a monomer (<b>3</b>) of [RuCp*<b>L</b>] (where <b>L</b>^<b>–</b> = 4,5-diazafluorenide) were prepared with the <b>L</b>^<b>–</b> ligand. The dimeric head-to-tail macrocycles [Cp*Ru­(L_pH)]₂Cl₂ (<b>4</b>) and [Cp*RuL_p]₂ (<b>5</b>) were obtained with the ditopic <b>L</b>_<b>p</b><b>H</b> and <b>L</b>_<b>p</b>^<b>–</b> ligands (where <b>L</b>_<b>p</b><b>H</b> = 9-(2-(diphenylphosphino)­ethyl)-4,5-diazafluorene and <b>L</b>_<b>p</b>^<b>–</b> = 9-(2-(diphenylphosphino)­ethyl)-4,5-diazafluorenide). The bulky arene-substituted <b>L</b>_<b>Mes</b><b>H</b> ligand (where <b>L</b>_<b>Mes</b><b>H</b> = 3,6-dimesityl-4,5-diazafluorene) was prepared, and its coordination to {RuCp*}⁺ gave [Cp*Ru­(<b>L</b>_<b>Mes</b><b>H</b>)]Cl (<b>13</b>). The selective syntheses of different linkage isomers of [RuCp*­(<b>L</b>_<b>Mes</b>)] (<b>14</b> and <b>15</b>) (where <b>L</b>_<b>Mes</b>^<b>–</b> = 3,6-dimesityl-4,5-diazafluorenide) were also demonstrated

Living bacteria inhibited human colonic smooth muscle contraction.

<p>The higher concentration (10¹⁰ CFUs/mL) obviously inhibited human colonic smooth muscle contraction compared with lower contractions (all <i>P</i><0.05). <i>E</i>. <i>faecalis</i> had the strongest inhibition compared with other probiotics (<i>P</i><0.05). N = 6 for each group.</p

Average size of tumor by the Fuhrman grade.

<p>Average size of tumor by the Fuhrman grade.</p

Distribution of the 2154 cases by year.

<p>Distribution of the 2154 cases by year.</p

Average tumor size by year.

<p>Average tumor size by year.</p

Distribution of the 2154 cases.

<p>Distribution of the 2154 cases.</p

The typical human colonic smooth muscle contraction response to the sterile CFS.

<p>Higher CFS concentrations produced a stronger inhibition of smooth muscle contraction. The MRS (de <i>Man-Rogosa-Sharpe</i> broth-sodium nitrite medium) was used as vacuity control.</p