Selective one-step synthesis of triple-decker (porphyrinato)(phthalocyaninato) early lanthanides: the balance of concurrent processes

An effective one-step approach for the preparation of (porphyrinato)(phthalocyaninato) early lanthanides of type [Br(4)TPP]Ln[(15C5)(4)Pc]Ln[Br(4)TPP], where Br(4)TPP = 5,10,15,20-tetrakis-(4-bromophenyl)-porphyrinato-ligand, (15C5)(4)Pc = tetrakis-(15-crown-5)-phthalocyaninato-ligand and Ln = La, Pr, Nd or Eu, is developed. The influence of various factors on the reaction pathway and yields of the complexes is investigated in detail. The developed protocol is found to be general for the early lanthanide subgroup. Variation of the synthetic conditions allowed the determination and isolation of possible side-products, namely heteroleptic double-deckers [Br(4)TPP]Ln[(15C5)(4)Pc] (Ln = Nd, Eu) and triple-decker [Br(4)TPP]Nd[(15C5)(4)Pc]Nd[(15C5)(4)Pc]. The peculiarities of the NMR lanthanide-induced shifts (LIS) of resonances of the synthesized triple-decker complexes are precisely investigated. The isostructurality of the synthesized complexes within the series as well as isostructurality with previously synthesized compounds is demonstrated in terms of two-nuclei analysis of LIS.     

NMR investigation of intramolecular dynamics of heteroleptic triple-decker (porphyrinato)(phthalocyaninato) lanthanides

Intramolecular dynamics of meso-aryl substituents of porphyrin deck in the triple-decker lanthanide (porphyrinato)(phthalocyaninates) of symmetrical type [Br(4)TPP]Ln[(15C5)(4)Pc]Ln[Br(4)TPP] (Ln = La, Nd, Eu; [Br(4)TPP] = tetrakis-5,10,15,20-(4-bromophenyl)-porphyrinato-ligand; [(15C5)(4)Pc] = tetrakis-(15-crown-5)-phthalocyaninato-ligand) are investigated. Attempts to achieve coalescence were not successful, although the trend of exchanging protons to coalescence point was observed in the case of Nd and Eu complexes. The analysis of NOESY cross-peaks between exchanging protons allowed to evaluate the rotation rate constants at different temperatures. The activation barrier of the meso-aryl substituent rotation was calculated with Arrhenius equation based on determined rate constants. The rate constants are lower and activation barriers are higher than ones found previously for related compounds.     

Novel approaches to model-free analysis of lanthanide-induced shifts, targeted to the investigation of contact term behavior

Three novel equations were proposed to perform graphical model-free analysis of lanthanide-induced shifts in NMR spectra of axially symmetrical complexes within Bleaney's T(-2) expansion. Application and efficiency of these newly developed approaches were demonstrated on the example of heteroleptic triple-decker crown-phthalocyaninates (Pc)M[(15C5)(4)Pc]M(Pc), where (15C5)--15-crown-5, (Pc(2-))--phthalocyaninato-dianion, M = Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb and Y as diamagnetic reference. By construction of these equations, the proposed analytical techniques are more sensitive to variations of hyperfine coupling terms throughout lanthanide series, in comparison with previously developed approaches, becoming a valuable tool for the investigation of structural and electronic characteristics of lanthanide complexes.     

周边硅笼取代的混杂酞菁卟啉三层铽单分子磁体

通过在铽的酞菁卟啉混杂三层的卟啉周边共价连接体积庞大的笼型倍半硅氧烷(POSS),得到了首个包含POSS的混 杂三层Tb₂(Pc)[T(OPOSS)₄PP]₂(1)[H₂Pc=phthalocyanine;H₂T(OPOSS)₄PP=5,10,15,20-tetra{[[N-[heptakis(isobutyl)propoxy]phenyl]octasiloxane]}porphyrin]。为了对比研究,同时合成了类似的三层化合物Tb₂(Pc)(TPP)₂(2)(H₂TPP=5,10,15,20-tetraphenyporphyrin)。尤其值得注意的是,在没有外加磁场的条件下,Tb₂(Pc)[T(OPOSS)₄PP]₂(1)和Tb₂(Pc)(TPP)₂(2)分别表现出单分子磁体和非单分子磁体的性质,这充分说明了共价连接均匀分布的POSS基团有效地分离了磁性核心,从而改善了酞菁卟啉混杂三层的磁性。     

Spectrophotometric study of the cation-induced dimerization of heteroleptic terbium(III) tetra-15-crown-5-bisphthalocyaninate

We proposed a new approach to the synthesis of heteroleptic crown-substituted terbium(III) bisphthalocyaninate, [(15C5)₄Pc]Tb(Pc) (1) based on the reaction of unsubstituted lanthanum bisphthalocyaninate (La(Pc)₂) with tetra-15-crown-5-phthalocyanine (H₂[(15C5)₄Pc]) and terbium(III) acetate in a mixture of octanol and chloronaphthalene in the presence of 1,8-diazabicyclo[ 5.4.0]undec-7-ene as an organic base. For the first time, we carried out a comparative spectrophotometric titration of compound 1 with MBPh₄ solutions (M = K, Rb, Cs) and demonstrated the formation of isostructural cofacial supramolecular dimers. Spectral-structural correlations were developed for evaluation of the distances between phthalocyanine ligands in new supramolecular assemblies, which can be used for the development of polynuclear suprasingle-molecule magnetic materials.

     

Effect of peripheral hydrophobic alkoxy substitution on the organic field effect transistor performance of amphiphilic tris(phthalocyaninato) europium triple-decker complexes

A series of four amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with different lengths of hydrophobic alkoxy substituents on one outer phthalocyanine ligand [Pc(15C5)4]Eu[Pc(15C5)4]Eu[Pc(OCnH(2n+1))8] (n = 4, 6, 10,12) (1, 2, 4, and 5) was designed and prepared. Their film forming and organic field effect transistor properties have been systematically studied in comparison with analogous [Pc(15C5)4]Eu[Pc(15C5)4]Eu[Pc(OC8H17)8] (3). Experimental results showed that all these typical amphiphilic sandwich triple-decker molecules have been fabricated into highly ordered films by the Langmuir-Blodgett (LB) technique, which displays carrier mobility in the direction parallel to the aromatic phthalocyanine rings in the range of 0.0032-0.60 cm2 V(-1) s(-1) depending on the length of the hydrophobic alkoxy substituents. This is rationalized on the basis of comparative morphology analysis results of the LB films by the atomic force microscopy technique.     

周边硅笼取代的混杂酞菁卟啉三层铽单分子磁体

通过在铽的酞菁卟啉混杂三层的卟啉周边共价连接体积庞大的笼型倍半硅氧烷(POSS), 得到了首个包含POSS的混杂三层Tb₂(Pc)[T(OPOSS)₄PP]₂ (1)[H₂Pc=phthalocyanine;H₂T(OPOSS)₄PP=5, 10, 15, 20-tetra{[[N-[heptakis(isobutyl)propoxy]phenyl]octasiloxane]}porphyrin]。为了对比研究, 同时合成了类似的三层化合物Tb₂(Pc)(TPP)₂(2)(H₂TPP=5,10,15,20-tetraphenyporphyrin)。尤其值得注意的是, 在没有外加磁场的条件下, Tb₂(Pc)[T(OPOSS)₄PP]₂(1)和Tb₂(Pc)(TPP)₂(2)分别表现出单分子磁体和非单分子磁体的性质, 这充分说明了共价连接均匀分布的POSS基团有效地分离了磁性核心, 从而改善了酞菁卟啉混杂三层的磁性。     

A novel efficient approach to heteronuclear triple-decker complexes of rare earth elements with phthalocyanines

A novel approach to heteroleptic heteronuclear rare earth metal(III) trisphthalocyaninates was proposed with the complexes [(15C5)₄Pc]M*[(15C5)₄Pc]M(Pc) as examples (15C5 is 15-crown-5, Pc^2? is the phthalocyaninate dianion, and M* ?? M = Yb and Y). Unsubstituted lanthanum bisphthalocyaninate, La(Pc)₂, was used for the first time as a Pc^2? donor in the synthesis of such complexes. This substantially increased the yields of the target heteronuclear complexes over the previous literature data.     

Synthesis, characterization, and OFET properties of amphiphilic heteroleptic tris(phthalocyaninato) europium(III) complexes with hydrophilic poly(oxyethylene) substituents

A series of amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with hydrophilic poly(oxyethylene) heads and hydrophobic alkoxy tails {Pc[(OC2H4)2OCH3]8}Eu{Pc[(OC2H4)2OCH3]8}Eu[Pc(OCnH2n + 1)8] (n = 6, 8, 10,12) (1-4) were designed and prepared from the reaction between homoleptic bis(phthalocyaninato) europium compound {Pc[(OC2H4)2OCH3]8}Eu{Pc[(OC2H4)2OCH3]8} and metal-free 2,3,9,10,16,17,23,24-octakis(alkoxy)phthalocyanine H2Pc(OCnH2n + 1)8 (n = 6, 8, 10,12) in the presence of Eu(acac)3.H2O (Hacac = acetylacetone) in boiling 1,2,4-trichlorobenzene (TCB). These novel sandwich triple-decker complexes have been characterized by a wide range of spectroscopic methods and have been electrochemically studied. With the help of the Langmuir-Blodgett (LB) technique, these typical amphiphilic triple-decker complexes have been fabricated into organic field effect transistors (OFET) with an unusual bottom contact configuration. The devices display good OFET performance with the carrier mobility for holes in the direction parallel to the aromatic phthalocyanine rings, which shows dependence on the length of the hydrophobic alkoxy side chains, decreasing from 0.46 for 1 to 0.014 cm2 V(-1) s(-1) for 4 along with the increase in the carbon number in the hydrophobic alkoxy side chains.     

Synthesis and structure of heteroleptic triple-decker neodymium,europium, holmium,erbium, and ytterbium crown phthalocyaninates

Two series of heteroleptic crown-substituted tris(phthalocyaninate) complexes (Pc)Ln[(15C5)₄Pc]Ln(Pc) and [(15C5)₄Pc]Ln[(15C5)₄Pc]Ln(Pc), where 15C5 is 15-crown-5, (Pc²⁻) is the phthalocyaninate dianion, Ln = Nd, Eu, Ho, Er, and Yb, were prepared by the reaction of tetra-15-crown-5-phthalocyanine H₂[(15C5)₄Pc] with the corresponding lanthanide acetylacetonates and lanthanum bis(phthalocyaninate) La(Pc)₂, which was used as a phthalocyaninate dianion donor. The composition and structure of the synthesized complexes were confirmed by MALDI TOF mass spectrometry, UV-Vis absorption spectroscopy, and ¹H NMR. Complete assignment of the proton resonance signals of the paramagnetic lanthanide complexes was based on analysis of lanthanide-induced shifts.     

Electron-donating alkoxy-group-driven synthesis of heteroleptic tris(phthalocyaninato) lanthanide(III) triple-deckers with symmetrical molecular structure

Reaction of heteroleptic bis(phthalocyaninato) lanthanide compounds [(Pc)M{Pc(OC8H17)8}] [H2Pc=unsubstituted phthalocyanine; H2Pc(OC8H17)8 = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine] with monomeric complexes [(Pc)M(acac)] (Hacac=acetylacetone), both of which generated in situ, led to the isolation of heteroleptic phthalocyaninato-[2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato] lanthainde(III) triple-decker complexes [(Pc)M{Pc(OC8H17)8}] (M=Gd-Lu) (1-8) as the sole product. Heterodinuclear analogues [(Pc)Lu{Pc(OC8H17)8}M(Pc)] (M=Gd-Yb) (9-15) were obtained in a similar manner from the reaction of [(Pc)M{Pc(OC8H17)8}] (M=Gd-Yb) and [(Pc)Lu(acac)]. The molecular structures of the herterodinuclear compound [(Pc)Lu{Pc(OC8H17)8}Er(Pc)] (13) and its homodinuclear counterparts [(Pc)M{Pc(OC8H17)8}M(Pc)] (M=Er, Lu) (5, 8) have been determined by X-ray diffraction analysis; these structures exhibit a symmetrical molecular structure with one inner planar Pc(OC8H17)8 ligand and two outer domed Pc ligands. In addition to various spectroscopic analyses, the electrochemistry of these compounds has also been studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods, revealing the gradually enhanced pi-pi interactions among the phthalocyanine rings in the triple-deckers along with the lanthanide contraction.     

Heteroleptic bis(phthalocyaninato) europium(III) complexes fused with different numbers of 15-crown-5 moieties. Synthesis, spectroscopy, electrochemistry, and supramolecular structure

A series of heteroleptic bis(phthalocyaninato) europium(III) complexes, namely, Eu(Pc)[Pc(15C5)] (2), Eu(Pc)[Pc(opp-15C5)2] (3), Eu(Pc)[Pc(adj-15C5)2] (4), Eu(Pc)[Pc(15C5)3] (5), and Eu(Pc)[Pc(15C5)4] (6) [Pc = unsubstituted phthalocyaninate; Pc(15C5) = 2,3-(15-crown-5)phthalocyaninate; Pc(opp-15C5)2 = 2,3,16,17-bis(15-crown-5)phthalocyaninate; Pc(adj-15C5)2 = 2,3,9,10-bis(15-crown-5)phthalocyaninate; Pc(15C5)3 = 2,3,9,10,16,17-tris(15-crown-5)phthalocyaninate, Pc(15C5)4 = 2,3,9,10,16,17,24,25-tetrakis(15-crown-5)phthalocyaninate], with one, two, three, and four 15-crown-5 voids attached at different positions of one of the two phthalocyaninato ligands in the double-decker molecules, have been devised and prepared by Eu(Pc)(acac)-induced (Hacac = acetylacetone) mixed cyclization of the two corresponding phthalonitriles in the presence of organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in n-pentanol. For the purpose of comparative studies, homoleptic counterparts Eu(Pc)2 (1) and Eu[Pc(15C5)4]2 (7) have also been prepared. These sandwich double-decker complexes have been characterized by a wide range of spectroscopic methods in addition to elemental analysis. Their electrochemistry has also been studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The molecular structure of Eu(Pc)[Pc(15C5)4] (6) has been determined by X-ray diffraction analysis. Their supramolecular structure-formation properties, in particular for compounds 5 and 6 in the presence of potassium ions, have also been comparatively studied for the purpose of future functional investigation.     

Chemistry of nitrosyliron complexes supported by a β-diketiminate ligand

Several nitrosyl complexes of Fe and Co have been prepared using the sterically hindered Ar-nacnac ligand (Ar-nacnac = anion of [(2,6-diisopropylphenyl)NC(Me)](2)CH). The dinitrosyliron complexes [Fe(NO)(2)(Ar-nacnac)] (1) and (Bu(4)N)[Fe(NO)(2)(Ar-nacnac)] (2) react with [Fe(III)(TPP)Cl] (TPP = tetraphenylporphine dianion) to generate [Fe(II)(NO)(TPP)] and the corresponding mononitrosyliron complexes. The factors governing NO transfer with dinitrosyliron complexes (DNICs) 1 and 2 are evaluated, together with the chemistry of the related mononitrosyliron complex, [Fe(NO)Br(Ar-nacnac)] (4). The synthesis and properties of the related cobalt dinitrosyl [Co(NO)(2)(Ar-nacnac)] (3) is also discussed for comparison to DNICs 1 and 2. The solid-state structures of several of these compounds as determined by X-ray crystallography are reported.     

Fourier transform ion cyclotron resonance studies of lanthanide(III) porphyrin-phthalocyanine heteroleptic sandwich complexes by using electrospray ionization

A number of neutral Ianthanide(III) porphyrin-phthalocyanine heteroleptic sandwich complexes have been studied by using positive-ion electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry. The investigated compounds are represented as Ln^III(TPP)(Pc), Ln ₂ ^III (TPP)(Pc)₂, and Ln ₂ ^III (TPP)₂(Pc), where Ln = Sm, Eu, or Gd, TPP is 5,10,15,20-tetraphenylporphyrinate, and Pc is phthalocyaninate. In all cases, intense signals corresponding to the singly charged molecular radical cations are observed. The formation of these molecular radical cations in electrospray ionization is attributed to electrochemical oxidation at the electrospray needle. Multiply charged molecular ions up to +5 are also observed. They are tentatively assigned to be formed from successive oxidation of the ligand(s). Apart from the molecular weight information, tandem mass spectrometry offers additional structural information on these complexes. From the fragmentation pattern of the europium complexes under collision-induced dissociation conditions, the configurations of the triple-decker complexes are assigned mass spectrometrically to be (TPP)Eu(Pc)Eu(Pc) and (TPP)Eu(Pc)Eu(TPP). In comparison with the previous spectroscopic findings that the positive “hole” is localized in the ligands of the complexes, there is evidence to suggest that intramolecular charge transfer or hole delocalization does occur within the macrocycles or between the metal centers and the macrocycles before fragmentation. The occurrence of this charge-transfer process is tentatively attributed to the result of collisional activation.     

Influence of Peripheral Substitution on the Magnetic Behavior of Single‐Ion Magnets Based on Homo‐ and Heteroleptic TbIII Bis(phthalocyaninate)

A series of homoleptic ([Tb^III(Pc)₂]) and heteroleptic ([Tb^III(Pc)(Pc′)]) Tb^III bis(phthalocyaninate) complexes that contain different peripheral substitution patterns (i.e., tert‐butyl or tert‐butylphenoxy groups) have been synthesized in their neutral radical forms and then reduced into their corresponding anionic forms as stable tetramethylammonium/tetrabutylammonium salts. All of these compounds were spectroscopically characterized and their magnetic susceptibility properties were investigated. As a general trend, the radical forms exhibited larger energy barriers for spin reversal than their corresponding reduced compounds. Remarkably, heteroleptic complexes that contain electron‐donor moieties on one of the two Pc ligands show higher effective barriers and blocking temperatures than their homoleptic derivatives. This result is assigned to the elongation of the N? Tb distances in the substituted macrocycle, which brings the terbium(III) ion closer to the unsubstituted Pc, thus enhancing the ligand‐field effect. In particular, heteroleptic [Tb^III(Pc)(Pc′)] complex 4 , which contains one octa(tert‐butylphenoxy)‐substituted Pc ring and one bare Pc ring, exhibits the highest effective barrier and blocking temperature for a single‐molecule magnet reported to date.     

Ferrocene-decorated (phthalocyaninato)(porphyrinato) double- and triple-decker rare earth complexes: synthesis, structure, and electrochemical properties

A series of four mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes (Pc)M[Por(Fc)(2)] [Pc = phthalocyaninate; Por(Fc)(2) = 5,15-di(ferrocenyl)-porphyrinate; M = Eu (1), Y (2), Ho (3), Lu (4)] and their europium(III) triple-decker counterpart (Pc)Eu(Pc)Eu[Por(Fc)(2)] (5), each with two ferrocenyl units at the meso-positions of their porphyrin ligands, have been designed and prepared. The double- and triple-decker complexes 1-5 were characterized by elemental analysis and various spectroscopic methods. The molecular structures of two double-deckers 1 and 4 were also determined by single-crystal X-ray diffraction analysis. Electrochemical studies of these novel sandwich complexes revealed two consecutive ferrocene-based one-electron oxidation waves, suggesting the effective electronic coupling between the two ferrocenyl units. Nevertheless, the separation between the two consecutive ferrocene-based oxidation waves increases from 1 to 4, along with the decrease of rare earth ionic radius, indicating the effect of rare earth size on tuning the coupling between the two ferrocenyl units. Furthermore, the splitting between the two ferrocene-based one-electron oxidations for triple-decker 5 is even smaller than that for 1, showing that the electronic interaction between the two ferrocene centers can also be tuned through changing the linking sandwich framework from double-decker to triple-decker. For further understanding of the electronic coupling between ferrocenyl groups, DFT calculation is carried out to clarify the electronic delocalization and the molecular orbital distribution in these double-decker complexes.     

Preparation, characterization, and theoretical analysis of group 14 element(I) dimers: a case study of magnesium(I) compounds as reducing agents in inorganic synthesis

A synthetic route to the new amidine (DipNH)(DipN)C(C(6)H(4)Bu(t)-4) (ButisoH; Dip = C(6)H(3)Pr(i)(2)-2,6) has been developed. Its deprotonation with either LiBu(n) or KN(SiMe(3))(2) yields the amidinate complexes [M(Butiso)] (M = Li or K). Their reactions with group 14 element halides/pseudohalides afford the heteroleptic group 14 complexes [(Butiso)SiCl(3)], [(Butiso)ECl] (E = Ge or Sn), and [{(Butiso)Pb(μ-O(3)SCF(3))(THF)}(∞)], all of which have been crystallographically characterized. In addition, the synthesis and spectroscopic characterization of the homoleptic complex [Pb(Butiso)(2)] is reported. Reductions of the heteroleptic complexes with a soluble magnesium(I) dimer, [{((Mes)Nacnac)Mg}(2)] ((Mes)Nacnac = [(MesNCMe)(2)CH](-); Mes = mesityl), have given moderate-to-high yields of the group 14 element(I) dimers [{(Butiso)E}(2)] (E = Si, Ge, or Sn), the X-ray crystallographic studies of which reveal trans-bent structures. The corresponding lead(I) complex could not be prepared. Comprehensive spectroscopic and theoretical analyses of [{(Butiso)E}(2)] have allowed their properties to be compared. All complexes possess E-E single bonds and can be considered as intramolecularly base-stabilized examples of ditetrelynes, REER. Taken as a whole, this study highlights the synthetic utility of soluble and easy to prepare magnesium(I) dimers as valuable alternatives to the harsh, and often insoluble, alkali-metal reducing agents that are currently widely employed in the synthesis of low-oxidation-state organometallic/inorganic complexes.     

Dinuclear single-molecule magnets with porphyrin-phthalocyanine mixed triple-decker ligand systems giving SAP and SP coordination polyhedra

Two terbium ions in a triple-decker complex (Pc)Tb(Pc)Tb(T(p-OMe)PP) (Pc = phthalocyaninato, T(p-OMe)PP = tetra-p-methoxyphenylporphyrinato) have shown sharply different magnetic behaviours depending on symmetry of the coordination polyhedron. The fast quantum tunnelling relaxation process in a square-prismatic site has been revealed to be hindered by magnetic-dipolar coupling between the f-electronic systems.     

Group 14 triple-decker cations

The triple-decker cations trans-[(Cp*Sn)(2)(mu-eta(5):eta(5)-Cp*)](+) and trans-[(Cp*Pb)(2)(mu-eta(5):eta(5)-Cp*)](+) have been prepared and structurally characterized as their [B(C(6)F(5))(4)](-) salts from the reactions of [Cp*M][B(C(6)F(5))(4)](M = Sn, Pb) with the appropriate decamethylmetallocene. Both triple-decker cations adopt a cisoid arrangement of terminal Cp* groups, whereas the two known triple-decker main-group anions possess a transoid arrangement of terminal Cp groups. The reason for this conformational difference has been probed on the basis of DFT calculations.     

Heteroleptic rare earth double-decker complexes with naphthalocyaninato and phthalocyaninato ligands. General synthesis, spectroscopic, and electrochemical characteristics

A novel one-pot procedure starting from the corresponding M(acac)3 x nH2O, metal-free phthalocyanine H2Pc', and naphthalonitrile in the presence of DBU in n-octanol has been developed to prepare heteroleptic (naphthalocyaninato)(phthalocyaninato) rare earth double-decker complexes. A series of six sandwich compounds with different naphthalocyaninato ligands, phthalocyaninato ligands, and central rare earth metals, namely, Sm[Nc(tBu)4](Pc) [Nc(tBu)4 = 3(4),12(13),21(22),30(31)-tetra(tert-butyl)naphthalocyaninato; Pc = unsubstituted phthalocyaninato] (1), Sm(Nc)(Pc') [Pc' = Pc(OC5H11)4, Pc(OC8H17)8; Nc = 2,3-naphthalocyaninato; Pc(OC5H11)4 = 2(3),9(10),16(17),24(25)-tetrakis(3-pentyloxy)phthalocyaninato; Pc(OC8H17)8 = 2,3,9,10,16,17,24,25-octakis(octyloxy)phthalocyaninato] (2, 3), and M(Nc)[Pc(alpha-OC5H11)4] [M = Sm, Eu, Y; Pc(alpha-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] (4-6), have been isolated in good yields from this one-pot procedure demonstrating the generality of this synthetic pathway. In addition to spectroscopic analyses, the electrochemistry of these novel compounds has also been studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods.