Double-decker Yttrium(III) Complexes with Phthalocyaninato and Porphyrinato Ligands

Abstract

<jats:p> A series of new yttrium(III) double-decker complexes with the same and different phthalocyaninato and porphyrinato ligands has been prepared. The homoleptic complexes Y ( P )<jats:sub>2</jats:sub> ( P = Pc *(C<jats:sub>7</jats:sub> H <jats:sub>15</jats:sub>)<jats:sub>8</jats:sub>, Pc *( OC <jats:sub>5</jats:sub> H <jats:sub>11</jats:sub>)<jats:sub>8</jats:sub>; Pc * = 2,3,9,10,16,17,23,24-octasubstituted phthalocyaninate) have been synthesized by treating yttrium(III) acetylacetonate ( Y ( acac )<jats:sub>3</jats:sub>· H <jats:sub>2</jats:sub> O ) with the phthalonitriles C <jats:sub>6</jats:sub> H <jats:sub>2</jats:sub> R <jats:sub>2</jats:sub>( CN )<jats:sub>2</jats:sub> ( R = C <jats:sub>7</jats:sub> H <jats:sub>15</jats:sub>, OC <jats:sub>5</jats:sub> H <jats:sub>11</jats:sub>) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The heteroleptic analogues Y ( P )( Pc ) ( P = Pc *( C <jats:sub>7</jats:sub> H <jats:sub>15</jats:sub>)<jats:sub>8</jats:sub>, Pc *( OC <jats:sub>5</jats:sub> H <jats:sub>11</jats:sub>)<jats:sub>8</jats:sub>; Pc = unsubstituted phthalocyaninate) and Y ( P )( Por ) ( P = Pc , Pc *( C <jats:sub>7</jats:sub> H <jats:sub>15</jats:sub>)<jats:sub>8</jats:sub>; Por = meso-tetraphenylporphyrinate (TPP), meso-tetra(4-pyridyl)porphyrinate (TPyP)) have been prepared by the base-catalysed tetramerization of the corresponding phthalonitriles using Y ( P )( acac ) ( P = Pc , TPP , TPyP ) as templates. The syntheses along with the spectroscopic and electrochemical properties of these novel double-deckers are described. </jats:p>

A series of homoleptic bis(phthalocyaninato) rare earth sandwich complexes with large two-photon absorption cross-section

“…The sandwich-type homoleptic substituted phthalocyaninato-rare earth [28][29]. The sandwich nature of these complexes has been confirmed by a wide range of spectroscopic methods including mass spectrometry, 1 H NMR, electronic absorption, and infra-red (IR) spectroscopy in addition to the elemental analysis [30][31][32][33][34].…”

Synthesis, spectroscopic properties and electrochemistry of (2,9,16,23-tetrasubstituted phthalocyaninato) erbium complexes

“…Due to the more electron-rich Pc(b-OC 5 H 11 ) 4 and Pc(b-C 4 H 9 ) 4 with respect to Pc, both the a 1u and e g orbitals of compounds 1 and 2 are higher than those of Pc. The former two similar absorptions at 450e465 and 920e950 nm are observed in the spectra of unsubstituted bis(phthalocyaninato)rare earth(III) complexes [M(Pc) 2 ] [18,19] and are assigned to the transitions from the fourth-occupied HOMO to the SOMO and from the SOMO to the LUMO, respectively [20]. The latter band at 1430e1450 nm is the transition between the second-highest occupied orbital and the semioccupied orbital [21].…”

Distribution of the unpaired electron in neutral bis(phthalocyaninato) yttrium double-deckers: An experimental and theoretical combinative investigation

“…All the bis(phthalocyaninato) yttrium complexes Y(Pc) 2 (1) (5) were prepared and isolated following the published procedures, which have been characterized by a series of spectroscopic methods in addition to elemental analysis [8][9][10][11].…”