Journal of Molecular Structure: THEOCHEM 717 (2005) 8589 www.elsevier.

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A comparison of structural and electronic characteristics among subphthalocyanine and phthalocyanine complexes
Dean Zdravkovski, M.C. Milletti*
Department of Chemistry, Eastern Michigan University, Ypsilanti, MI 48197, USA Received 12 May 2004; revised 23 July 2004; accepted 19 August 2004 Available online 22 January 2005

Abstract Molecular orbital calculations are used to analyze factors that lead to structural differences among a series of four subphthalocyanine and two phthalocyanine complexes. The effects of changing the central atom from boron to aluminum and from carbon to silicon are elucidated for the corresponding subphthalocyanine complexes. In addition, carbon and silicon phthalocyanine complexes are compared. Results of the calculations suggest that the complexes assume a concave or planar conformation depending on the relative size of the central atom and the cavity, irrespective of electronic factors. The nature of the bonding between the central atom and the subphthalocyanine macrocycle is also investigated. q 2004 Elsevier B.V. All rights reserved.
Keywords: Phthalocyanine; Subphthalocyanine; Structure; Density functional theory

1. Introduction Subphthalocyanines are a group of boron-containing compounds, rst synthesized in 1972 by Meller and Ossko [1]. They are composed of three diiminoisoindole rings N-fused around a boron core [2] and represent the lowest homologues of phthalocyanines, well known two-dimensional 18 p-electron aromatic systems [3]. Research on subphthalocyanines remained fairly untouched until 1990 when the tri-t-butyl macrocycle, BsubPc(t-Bu)3Br, was described by Kobayashi et al. [4]. The interest in subphthalocyanine (SubPc) macrocycles suddenly grew a great deal because of their use as starting materials in the synthesis of unsymmetrical phthalocyanines [5] and, more recently, materials that have particularly high non-linear optical sensitivity in second-harmonic (SHG) and thirdharmonic generation (THG) [6]. Only the boron derivatives of these compounds are known and their structure is nonplanar [4]. In contrast, the related phthalocyanines (Pcs) usually exhibit a at structure. However, it is known that the degree
* Corresponding author. Tel.: C1 734 487 1183; fax: C1 734 487 1496. E-mail address: mmilletti@emich.edu (M.C. Milletti). 0166-1280/$ - see front matter q 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.theochem.2004.08.043

of planarity of the macrocycle is highly dependent on the size of the cavity of the macrocycle, as well as the radius of the central atom. For example, metalloPcs (MtPcs) such as unsubstituted NiPc are highly planar [7], but others with large atomic radii (Sn, Pb) have a distorted geometry [8]. The goal of this work is to elucidate the role of the identity of the central atom in determining the degree of planarity of the macrocycle. Specically, geometry optimization calculations are used to determine how the central atom ts in the macrocycle cavity, in terms of both size and bonding. Two macrocycle sizes are used: three-unit subphthalocyanine and four-unit phthalocyanine. Four central atoms are investigated: carbon and silicon (Group IV) and boron and aluminum (Group III).

2. Details of the calculations All calculations were carried out using Density Functional Theory [9]. Specically, Beckes three-parameter exchange functional (B3) was used in conjunction with the LeeYangParr correlation functional (LYP) at the 6-21G basis set level [10]. The initial geometry for each molecule was created with Gauss View 98 W [11] and subsequent

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Table 1 Comparison of cavity size vs. size of the central atom for all four subphthalocyanine complexes Cavity sizea (A2) BsubPc AlSubPc CSubPc SiSubPc
a b

Covalent radius of the central atom (A) 0.88 1.43 0.77 1.17

NX bond distance in cavity (A) 1.5 1.51 1.32 1.98

Normal NX bond distanceb (A) 1.42 1.83 1.35 1.57

2.43 2.97 2.22 2.74

Cavity size is the two-dimensional area comprised by the three N atoms. CRC Handbook of Chemistry and Physics, 66th edition, 1985.

molecular orbital calculations were carried out using GAUSSIAN 94 [12] and GAUSSIAN 98 [13]. To make sure that the choice of initial geometry would not determine the structure of the optimized complex (in other words, to prevent the calculation from falling in the nearest local minimum) optimization calculation for each complex were started with both a planar (at) and a concave (bowl) initial geometry. Each structure was subsequently optimized using the Berny algorithm [14] at the B3LYP/ 6-21G level (See Table 1). The 6-21G basis set level was used because it allowed for the calculations to be completed within a reasonable amount of computational time. Since this basis set is smaller than the more commonly used 6-31G, which has been shown to reproduce experimental geometrical parameters well [15], one set of calculations was also carried out at the 6-31G basis set level. Specically, calculations for subphthalocyanine with Si as the central atom were carried out with both basis sets, starting with the planar and concave congurations. In both cases the structure optimized to the same minimum.

3. Results and discussion Boron subphthalocyanine is known to have a bowl-like conformation [16]. In this work, we examine the effect of changing the central atom on the conformation of the macrocycle. Central atoms with three valence electrons (boron and aluminum) are compared to atoms with four valence electrons (carbon and silicon). Atoms of different size are also compared: boron (second period) vs. aluminum (third period) and carbon (second period) vs. silicon (third period).

Fig. 1. A comparison of total energies for initial and optimized structures of the four subphthalocyanine molecules.

Fig. 2. Optimized structures for the four subphthalocyanine molecules. The grey spheres are carbon atoms, blue ones are nitrogen, aluminum and boron are pink, and silicon is grey blue. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article).

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Fig. 3. Mulliken overlap populations for selected bonds in CSubPc and SiSubPc.

For all subphthalocyanine molecules, geometry optimization calculations were started from both a concave structure and a planar structure. In all cases, except for the compounds where carbon is the central atom, the molecule optimizes to the concave structure. For carbon subphthalocyanine, both structures are stable, but the one where the macrocycle is at is thermodynamically more stable (see Fig. 1). Optimized structures for each of the four atoms with a subphthalocyanine macrocycle are shown in Fig. 2. Clearly, all molecules have a bowl-like conformation, except for the carbon one. This is supported by crystal diffraction data [17]. The preferred conformations that are observed can be explained in terms of size of the cavity and radius of the central atom. Table 1 shows the size of the cavity in each of the optimized structures above and the radius of the corresponding central atom. The size of the cavity was taken as the area comprised by the nitrogen atoms bonded to the central atom. The third column in the table indicates the bond distance between the central atom and the closest set of nitrogen atoms in the optimized structure, while the fourth column lists the normal element nitrogen bond distance. The data in Table 1 indicates that the difference between the normal atom-to-nitrogen bond distance and the distance in the cavity is signicant for all complexes, but CSubPc. Therefore, carbon is the only central atom that has the perfect size to t in the cavity when the macrocycle is planar. To further examine the reasons for the different congurations of the macrocycles, a Mulliken population analysis [18] was performed on the planar subphthalocyanine carbon and the concave silicon subphthalocyanine. Mulliken overlap populations for each bond are shown in Fig. 3. Overlap populations for the outer aromatic rings are essentially the same in both molecules. However, the bond between the central atom (C or Si) and the three nitrogen atoms of the macrocycle is much stronger for carbon than for silicon. This in turn affects the strength of the bonds between the nitrogen atoms and the adjacent carbon atoms

Fig. 4. Optimized structures for the two phthalocyanine molecules.

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Table 2 Comparison of cavity size vs. size of the central atom for the two phthalocyanine complexes Cavity size (A2) CPc SiPc 8.16 7.67 Radius of the central atom (A) 0.77 1.17 NX bond distance in cavity (A) 1.39 and 2.59 2.12 Normal NX bond distance (A) 1.35 1.57

4. Conclusions The results obtained from the calculations performed on the subphthalocyanine complexes show that the concave shape of the complexes is mainly due to the size of the central atom: the atom with the smallest atomic radius, carbon, is the perfect size for the subphthalocyanine cavity, resulting in a planar conformation. On the other hand, the radii of boron, aluminum and silicon are signicantly larger, resulting in a concave conformation. The same general conclusion can be drawn about the phthalocyanine complexes: SiPc is bowl shaped because of the larger size of the central atom, while CPc is planar, with the carbon atom only bonded to one side of the cavity.

Acknowledgements We thank the supercomputing center at the University of Texas for use of their CRAY SV1 Supercomputer and Dr Vance Kennedy for many helpful discussions.

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Fig. 5. Partial charges for selected atoms of carbon phthalocyanine.

in the macrocycle (much weaker in the carbon complex than in the silicon complex). Calculations were also carried out for the four-unit phthalocyanine molecule with C and Si as central atoms, since both of these atoms have four valence electrons. Obviously, the macrocycle cavity is larger in this case and the silicon atom has no trouble tting in a planar cavity, as shown in Fig. 4. On the other hand, the carbon atom is too small and it actually bonds to only one side of the cavity (see Table 2). This leads to a propeller-like structure (also shown in Fig. 4), which matches experimental evidence [19]. Bond lengths in the optimized structure for the carbon phthalocyanine suggest that the carbon atom forms single bonds only with two of the four surrounding nitrogen atoms. This is further supported by the fact that the nitrogen atoms bonded to the carbon atom have a much more negative partial charge than the nitrogen atoms on the opposite side of the macrocycle (see Fig. 5). Finally the overlap population data indicates that the two CN bonds are single bonds: there are approximately 0.16 eK in the overlap region, while there are 0.43 eK in the overlap region of the CaN bonds in the same molecule.

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