The intramolecular carbene-carbonyl coupling has been investigated for the simple M(CH<sub>2</sub>)(CO)<sub>3</sub> (M = Co, Rh, Ir) radical complexes at the DFT PBEPBE/TZVP level of theory. The coupling is predicted to be very fast for the cobalt-containing system, but it is still feasible for the systems based on the other two metals. The back-way reaction, that is, the conversion of the ketene complex into carbonyl-carbene complex, cannot be excluded from the Ir-containing system in CH<sub>2</sub>Cl<sub>2</sub>, and it is even favored in gas phase. The intermolecular ketene formation by the addition of external CO onto the CH<sub>2</sub> moiety is the favored pathway for the Ir-complex. The Laplacian distribution, as well as the natural spin density distribution of all the species, being involved in the reaction, gives explanation for the significant difference between the nature of the Co-complex and the Rh- and Ir-systems.

G&#xe1;bor Toll&#xe1;r

Tam&#xe1;s K&#xe9;gl

Computational Study on the Intramolecular Carbene-CO Coupling in M(CH<sub>2</sub>)(CO)<sub>3</sub> Radicals (M = Co, Rh, Ir)

With the aim of directing lanthanide complex uptake via the mannose receptor, a first generation of luminescent lanthanide complexes has been developed with an <i>&#x3b1;</i>-D-mannose targeting motif. Four complexes were produced to investigate photophysical properties and determine the effect of the coordinated mannose residue on emission intensity. The free hydroxyls of the <i>&#x3b1;</i>-D-mannose residue quenched lanthanide phosphorescence due to their close proximity, though they did not bind the lanthanide centre as observed by <i>q</i>-values <i>&#x2248;</i>1.0 for all complexes between pH 3 and 10. Fluorescent emission was found to vary significantly with pH, though phosphorescent emission was relatively insensitive to pH. This lack of pH sensitivity has the potential to provide stable emission for the visualisation of the endosome-lysosome system where acidic pH is often encountered.

Robert Brooks

Zhangli Du

Glenn Borlace

Douglas Brooks

Sally Plush

Synthesis and Characterisation of First Generation Luminescent Lanthanide Complexes Suitable for Being Adapted for Uptake via the Mannose Receptor

4,4&#x2032;-Diaminobiphenyl reacts with 2,4-pentanedione in absolute ethanol in a molar ratio 1&#x2009;:&#x2009;2 to form mainly the product of [1 + 2] condensation, 4,4&#x2032;-(biphenyl-4,4&#x2032;-diyldinitrilo)dipentan-2-one (H<sub  >2</sub>L). The Schiff base was used as tetradentate chelating ligand to coordinate <svg     style="vertical-align:-0.20473pt;width:29.0875px;" id="M2" height="16.275" version="1.1" viewBox="0 0 29.0875 16.275" width="29.0875"  xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg">
	
		
			<g transform="matrix(.017,-0,0,-.017,.062,15.95)"><path id="x43" d="M614 175l29 -10q-33 -109 -57 -154q-121 -26 -184 -26q-90 0 -160.5 29t-112.5 77t-63.5 105.5t-21.5 119.5q0 157 108 253t277 96q36 0 71.5 -5t69 -13.5t36.5 -8.5q15 -102 20 -150l-29 -8q-20 79 -66.5 114t-128.5 35q-119 0 -187.5 -86t-68.5 -207&#xA;q0 -140 73.5 -227.5t188.5 -87.5q73 0 119.5 37.5t86.5 116.5z" /></g><g transform="matrix(.017,-0,0,-.017,11.605,15.95)"><path id="x6F" d="M257 449q92 0 154 -65t62 -158q0 -112 -67 -175t-150 -63q-98 0 -158.5 66.5t-60.5 154.5q0 59 21 106.5t54.5 75.5t71 43t73.5 15zM244 416q-48 0 -81 -47t-33 -128q0 -96 38 -158t99 -62q51 0 82 43.5t31 139.5q0 91 -36 151.5t-100 60.5z" /></g>

			<g transform="matrix(.012,-0,0,-.012,20.287,7.8)"><path id="x49" d="M303 0h-265v28q62 5 76 19.5t14 77.5v400q0 63 -14 77.5t-76 19.5v28h265v-28q-62 -5 -76 -19.5t-14 -77.5v-400q0 -64 14 -78t76 -19v-28z" /></g><g transform="matrix(.012,-0,0,-.012,24.345,7.8)"><use xlink:href="#x49"/></g>

		
	
</svg> and <svg     style="vertical-align:-0.12283pt;width:25.6875px;" id="M3" height="16.174999" version="1.1" viewBox="0 0 25.6875 16.174999" width="25.6875"  xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg">
	
		
			<g transform="matrix(.017,-0,0,-.017,.062,15.95)"><use xlink:href="#x4E"/></g><g transform="matrix(.017,-0,0,-.017,12.336,15.95)"><path id="x69" d="M135 536q-20 0 -35 15.5t-15 35.5q0 22 15 37t36 15t35.5 -15t14.5 -37q0 -21 -15 -36t-36 -15zM252 0h-220v26q48 5 59 17t11 63v206q0 47 -9 58t-54 18v24q78 12 142 39v-345q0 -51 11.5 -63t59.5 -17v-26z" /></g>

			<g transform="matrix(.012,-0,0,-.012,16.887,7.8)"><use xlink:href="#x49"/></g><g transform="matrix(.012,-0,0,-.012,20.945,7.8)"><use xlink:href="#x49"/></g>

		
	
</svg> chlorides leading to complexes where the ratio of metal ligand was found to be 2&#x2009;:&#x2009;1 or 2&#x2009;:&#x2009;2. All the synthesized products were characterized by elemental analysis, infrared, electronic, and mass spectroscopy, <sup  >1</sup>H NMR, and DSC. The electrochemical behaviour of the ligand and its complexes in DMF is also investigated.

Lakhdar Sibous

Embarek Bentouhami

Mustayeen Ahmed Khan

Synthesis, Characterization, and Electrochemical Behaviour of Cobalt(II) and Nickel(II) Complexes with <svg style="vertical-align:-3.27605pt" height="15.5125" version="1.1" viewBox="0 0 38.599998 15.5125" width="38.599998" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg"><g transform="matrix(.017,-0,0,-.017,.062,11.363)"><path id="x4E" d="M719 650v-28q-43 -2 -62 -15t-22 -44q-6 -47 -6 -169v-403h-31l-426 524h-2v-251q0 -111 6 -169q4 -37 24 -50.5t72 -16.5v-28h-237v28q45 2 64.5 16t23.5 49q6 62 6 171v220q0 54 -3 68.5t-17 32.5q-16 19 -34.5 26.5t-54.5 10.5v28h147l418 -502h3v246q0 117 -7 166&#xA;q-4 34 -24.5 47t-73.5 15v28h236z" /></g><g transform="matrix(.012,-0,0,-.012,12.687,15.45)"><path id="x1D7D0" d="M453 211h25l-46 -211h-415v23q97 102 151 166q42 49 81 110q51 78 51 148q0 56 -31.5 91.5t-87.5 35.5q-77 0 -122 -90h-28q67 204 223 204q82 0 132 -49.5t50 -133.5q0 -110 -114 -218l-162 -154h140q82 0 107 13q27 13 46 65z" /></g><g transform="matrix(.017,-0,0,-.017,19.262,11.363)"><path id="x4F" d="M381 665q131 0 226.5 -93t95.5 -239q0 -158 -96 -253t-238 -95q-137 0 -231 95t-94 238q0 142 92.5 244.5t244.5 102.5zM359 629q-89 0 -151 -74.5t-62 -208.5q0 -141 69 -233t175 -92q90 0 150.5 74t60.5 211q0 152 -69 237.5t-173 85.5z" /></g><g transform="matrix(.012,-0,0,-.012,31.962,15.45)"><use xlink:href="#x1D7D0"/></g></svg> Chelating Ligand 4,4&#x2032;-(Biphenyl-4,4&#x2032;-diyldinitrilo)dipentan-2-one

Some oxovanadium(IV) complexes of SA/SSA and 5, 10, 15, and 20-meso-tetraphenylporphyrin (H<sub>2</sub>tpp) with unidentate and bidentate nitrogen donors have been synthesized and characterized by elemental analysis, conductivity measurements, magnetic susceptibility, UV-Vis, IR, mass spectroscopy, TGA/DTA, and <sup>1</sup>H, <sup>13</sup>C and <sup>51</sup>V NMR studies to investigate the steric and electronic effects of axial ligands on the properties of porphyrins. On the basis of these studies, it has been investigated that the axial ligands bind to the sixth coordination site of the vanadium ion to form a relatively stable six-coordinate-porphyrin complex where as in the case of SA/SSA complexes the nitrogen donors bind to the equatorial position giving  square pyramidal geometry. The <i>in vitro</i> cytotoxicity against human cancer cell lines and antimicrobial activities of the synthesized compounds have been done against various fungal and bacterial pathogens. The [VO(SA/SSA)L/L-L] complexes were found to possess higher antibacterial, antifungal activity and <i>in vitro</i> cytotoxicity against human cancer cell lines than VO(tpp)L complexes.

Gauri D. Bajju

Puja Sharma

Ashu Kapahi

Madhulika Bhagat

Sujata Kundan

Deepmala Gupta

Oxovanadium(IV) Complexes with Nitrogen Donors: Synthesis, Characterisation, and Biological Activities

Polyoxometalates were grafted covalently on SBA-15 by a two-step procedure. The dehydroxylated mesoporous silica was first modified by reaction with methyltrichlorosilane in presence of triethylamine. The resulting solid was fully characterized and contained a mixture of mono- and digrafted species <svg     style="vertical-align:-3.3907pt;width:137.08749px;" id="M1" height="16.450001" version="1.1" viewBox="0 0 137.08749 16.450001" width="137.08749"  xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg">
	
		
			<g transform="matrix(.017,-0,0,-.017,.062,12.162)"><path id="x28" d="M300 -147l-18 -23q-106 71 -159 185.5t-53 254.5v1q0 139 53 252.5t159 186.5l18 -24q-74 -62 -115.5 -173.5t-41.5 -242.5q0 -130 41.5 -242.5t115.5 -174.5z" /></g><g transform="matrix(.017,-0,0,-.017,5.944,12.162)"><path id="x2261" d="M535 397h-483v50h483v-50zM535 230h-483v50h483v-50zM535 63h-483v50h483v-50z" /></g><g transform="matrix(.017,-0,0,-.017,20.631,12.162)"><path id="x53" d="M409 504l-29 -5q-16 60 -44.5 96t-86.5 36q-54 0 -82.5 -32t-28.5 -77q0 -51 30.5 -82.5t96.5 -65.5l35.5 -18t33 -19.5t33.5 -23.5l27 -25.5t24.5 -32t13.5 -36.5t6 -45q0 -80 -62 -134.5t-160 -54.5q-47 0 -98 15q-22 7 -50 21q-8 23 -27 155l30 7q7 -27 18 -52&#xA;t30 -51.5t49 -42.5t67 -16q56 0 88 32.5t32 87.5q0 51 -31.5 82t-98.5 67q-80 44 -110 73q-55 53 -55 124q0 75 56 126.5t150 51.5q53 0 126 -23z" /></g><g transform="matrix(.017,-0,0,-.017,28.603,12.162)"><path id="x69" d="M135 536q-20 0 -35 15.5t-15 35.5q0 22 15 37t36 15t35.5 -15t14.5 -37q0 -21 -15 -36t-36 -15zM252 0h-220v26q48 5 59 17t11 63v206q0 47 -9 58t-54 18v24q78 12 142 39v-345q0 -51 11.5 -63t59.5 -17v-26z" /></g><g transform="matrix(.017,-0,0,-.017,33.159,12.162)"><path id="x2D" d="M300 253l-14 -55h-229l14 55h229z" /></g><g transform="matrix(.017,-0,0,-.017,36.389,12.162)"><use xlink:href="#x2D"/></g><g transform="matrix(.017,-0,0,-.017,42.44,12.162)"><path id="x4F" d="M381 665q131 0 226.5 -93t95.5 -239q0 -158 -96 -253t-238 -95q-137 0 -231 95t-94 238q0 142 92.5 244.5t244.5 102.5zM359 629q-89 0 -151 -74.5t-62 -208.5q0 -141 69 -233t175 -92q90 0 150.5 74t60.5 211q0 152 -69 237.5t-173 85.5z" /></g><g transform="matrix(.017,-0,0,-.017,55.138,12.162)"><path id="x29" d="M275 270q0 -296 -211 -440l-19 23q75 62 116.5 174t41.5 243t-42 243t-116 173l19 24q211 -144 211 -440z" /></g>

			<g transform="matrix(.012,-0,0,-.012,61,16.25)"><path id="x1D45B" d="M495 86q-46 -47 -87 -72.5t-63 -25.5q-43 0 -16 107l49 210q7 34 8 50.5t-3 21t-13 4.5q-35 0 -109.5 -72.5t-115.5 -140.5q-21 -75 -38 -159q-50 -10 -76 -21l-6 8l84 340q8 35 -4 35q-17 0 -67 -46l-15 26q44 44 85.5 70.5t64.5 26.5q35 0 10 -103l-24 -98h2&#xA;q42 56 97 103.5t96 71.5q46 26 74 26q9 0 16 -2.5t14 -11.5t9.5 -24.5t-1 -44t-13.5 -68.5q-30 -117 -47 -200q-4 -19 -3.5 -25t6.5 -6q21 0 70 48z" /></g>

			<g transform="matrix(.017,-0,0,-.017,67.6,12.162)"><use xlink:href="#x53"/></g><g transform="matrix(.017,-0,0,-.017,75.572,12.162)"><use xlink:href="#x69"/></g><g transform="matrix(.017,-0,0,-.017,80.128,12.162)"><path id="x4D" d="M861 0h-263v28q61 5 73 22t12 97l-4 408h-4l-244 -548h-20l-224 534h-2l-15 -285q-5 -98 -3 -166q1 -34 19.5 -45t72.5 -17v-28h-233v28q45 5 62.5 17t22.5 43q11 65 19 183l14 208q3 36 3.5 55t-2.5 37.5t-6.5 25t-16.5 13t-25.5 8t-39.5 4.5v28h164l228 -501l232 501&#xA;h170v-28q-68 -6 -81 -21.5t-11 -91.5l9 -362q2 -80 15 -97t78 -22v-28z" /></g><g transform="matrix(.017,-0,0,-.017,94.832,12.162)"><path id="x65" d="M380 106l15 -22q-42 -52 -87 -74t-76 -22q-89 0 -142 62t-53 151q0 103 66 175q67 73 146 73h1q61 0 105.5 -46.5t44.5 -105.5q0 -16 -4.5 -22.5t-18.5 -9.5q-54 -10 -262 -17q1 -95 46 -143.5t104 -48.5q61 0 115 50zM225 412q-35 0 -64.5 -32.5t-40.5 -90.5q83 0 170 3&#xA;q14 0 19 4.5t5 15.5q1 41 -23.5 70.5t-65.5 29.5z" /></g><g transform="matrix(.017,-0,0,-.017,102.056,12.162)"><path id="x43" d="M614 175l29 -10q-33 -109 -57 -154q-121 -26 -184 -26q-90 0 -160.5 29t-112.5 77t-63.5 105.5t-21.5 119.5q0 157 108 253t277 96q36 0 71.5 -5t69 -13.5t36.5 -8.5q15 -102 20 -150l-29 -8q-20 79 -66.5 114t-128.5 35q-119 0 -187.5 -86t-68.5 -207&#xA;q0 -140 73.5 -227.5t188.5 -87.5q73 0 119.5 37.5t86.5 116.5z" /></g><g transform="matrix(.017,-0,0,-.017,113.429,12.162)"><path id="x6C" d="M238 0h-223v26q48 5 60 17t12 61v473q0 50 -10.5 60.5t-58.5 15.5v24q73 8 148 35v-608q0 -49 11.5 -61t60.5 -17v-26z" /></g>

			<g transform="matrix(.012,-0,0,-.012,117.725,16.25)"><path id="x33" d="M285 378v-2q65 -13 102 -54.5t37 -97.5q0 -57 -30.5 -104.5t-74 -75t-85.5 -42t-72 -14.5q-31 0 -59.5 11t-40.5 23q-19 18 -16 36q1 16 23 33q13 10 24 0q58 -51 124 -51q55 0 88 40t33 112q0 64 -39 96.5t-88 32.5q-29 0 -64 -11l-6 29q77 25 118 57.5t41 84.5&#xA;q0 45 -26.5 69.5t-68.5 24.5q-67 0 -120 -79l-20 20l43 63q51 56 127 56h1q66 0 107 -37t41 -95q0 -42 -31 -71q-22 -23 -68 -54z" /></g><g transform="matrix(.012,-0,0,-.012,123.436,16.25)"><path id="x2212" d="M535 230h-483v50h483v-50z" /></g><g transform="matrix(.012,-0,0,-.012,130.421,16.25)"><use xlink:href="#x1D45B"/></g>

		
	
</svg>. These surface Si&#x2013;Cl bonds can react with lacunary polyoxometalates as in solution, yielding to a <i  >&#x2261;</i>Si&#x2013;O&#x2013;POM linkage. However, solid state MAS NMR shows that only the digrafted species react with the polyoxometalate. This new grafting method opens the way to the synthesis of a new class of catalysts which could operate in solution without leaching.

Eva Grinenval

Jean-Marie Basset

Fr&#xe9;d&#xe9;ric Lefebvre

A Novel Approach to Prepare Well-Defined Silica-Supported Polyoxometalate Species by Reaction with a Chlorinated Support

Three two-dimensional (2D) and 3D supramolecular coordination architectures based on ternary M(II)-dicyanamide-2-hydroxypyridine systems, [Co(hmpH)<sub  >2</sub>(dca)<sub  >2</sub>] (<b  >1</b>), [Cu(hmpH)<sub  >2</sub>(dca)<sub  >2</sub>] (<b  >2</b>), and [Mn(hepH)<sub  >2</sub>(dca)<sub  >2</sub>] (<b  >3</b>) (dca = dicyanamide, hmpH = 2-(hydroxymethyl)pyridine, hepH = 2-(hydroxyethyl)pyridine), have been synthesized. <b  >1</b> is a mononuclear Co(II) complex. The mononuclear units are interlinked into a 2D (4,4) hydrogen-bonded layer via O&#x2013;H<i>&#x22ef;</i>N hydrogen bonds between the hydroxyl groups and the noncoordinating nitrile ends. These 2D layers are further extended into a 3D supramolecular architecture via the interlayer pyridyl-pyridyl stacking interaction. <b  >2</b> has a 1D coordination chain structure formed by the double <svg     style="vertical-align:-3.56265pt;width:9.5625px;" id="M1" height="12.175" version="1.1" viewBox="0 0 9.5625 12.175" width="9.5625"  xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg">
	
		
			<g transform="matrix(.017,-0,0,-.017,.062,7.675)"><path id="x1D707" d="M538 96q-38 -45 -84 -76.5t-71 -31.5q-44 0 -15 117q12 49 18 89h-2q-99 -128 -163 -178q-36 -28 -70 -28q-26 0 -44 38h-2q-16 -69 -16 -129q0 -43 11 -75.5t24 -42.5l1 -6q-7 -12 -24.5 -23t-37.5 -11q-40 0 -40 76q0 52 35 202l94 407l78 24l5 -5q-32 -122 -72 -310&#xA;q-7 -33 0 -55t25 -22q36 0 105.5 75t107.5 145l32 146l75 26h10q-50 -197 -78 -347q-7 -38 6 -38q7 0 31 17t47 39z" /></g>

		
	
</svg><sub  >1,5</sub>-dca bridged dinuclear [Cu2(<svg     style="vertical-align:-3.56265pt;width:9.5625px;" id="M2" height="12.175" version="1.1" viewBox="0 0 9.5625 12.175" width="9.5625"  xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg">
	
		
			<g transform="matrix(.017,-0,0,-.017,.062,7.675)"><use xlink:href="#x1D707"/></g>

		
	
</svg><sub  >1,5</sub>-dca)<sub  >2</sub>(hmpH)<sub  >2</sub>] unit and the <svg     style="vertical-align:-3.56265pt;width:9.5625px;" id="M3" height="12.175" version="1.1" viewBox="0 0 9.5625 12.175" width="9.5625"  xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg">
	
		
			<g transform="matrix(.017,-0,0,-.017,.062,7.675)"><use xlink:href="#x1D707"/></g>

		
	
</svg><sub  >1,3</sub>-dca bridges via weak Cu&#x2013;N coordination, and these 1D coordination chains are further extended into 2D hydrogen-bonded layers via strong O&#x2013;H<i  >&#x22ef;</i>N hydrogen-bonding interaction between the hydroxyl groups and the noncoordinating nitrile ends. <b  >3</b> is a 2D (4,4) coordination network made of 1D [Mn(hepH)(<svg     style="vertical-align:-3.56265pt;width:9.5625px;" id="M4" height="12.175" version="1.1" viewBox="0 0 9.5625 12.175" width="9.5625"  xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg">
	
		
			<g transform="matrix(.017,-0,0,-.017,.062,7.675)"><use xlink:href="#x1D707"/></g>

		
	
</svg><sub  >1,5</sub>-dca)] helical chain units and interchain double (<svg     style="vertical-align:-3.56265pt;width:9.5625px;" id="M5" height="12.175" version="1.1" viewBox="0 0 9.5625 12.175" width="9.5625"  xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg">
	
		
			<g transform="matrix(.017,-0,0,-.017,.062,7.675)"><use xlink:href="#x1D707"/></g>

		
	
</svg><sub  >1,5</sub>-dca) bridges. Pairs of [Mn(hepH)(<svg     style="vertical-align:-3.56265pt;width:9.5625px;" id="M6" height="12.175" version="1.1" viewBox="0 0 9.5625 12.175" width="9.5625"  xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg">
	
		
			<g transform="matrix(.017,-0,0,-.017,.062,7.675)"><use xlink:href="#x1D707"/></g>

		
	
</svg><sub  >1,5</sub>-dca)] helical chains are interlinked by the double (<svg     style="vertical-align:-3.56265pt;width:9.5625px;" id="M7" height="12.175" version="1.1" viewBox="0 0 9.5625 12.175" width="9.5625"  xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg">
	
		
			<g transform="matrix(.017,-0,0,-.017,.062,7.675)"><use xlink:href="#x1D707"/></g>

		
	
</svg><sub  >1,5</sub>-dca) bridges into a racemic coordination layer structure, which is further extended into a 3D hydrogen-bonded network. Magnetic studies reveal that weak antiferromagnetic exchange occurs in <b  >3</b>.

Ling-Ling Zheng

Synthesis, Crystal Structures, and Magnetic Properties of Ternary M(II)-Dicyanamide-hydroxypyridine Complexes

About this journal

Journal profile

Meet the editorial board

Editor spotlight

Find out more

This journal's articles appear in a wide range of abstracting and indexing databases, and are covered by numerous other services that aid discovery and access. Find out more about where and how the content of this journal is available.

Journal of Inorganic Chemistry