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Template-controlled on-surface synthesis of a lanthanide supernaphthalocyanine and its open-chain polycyanine counterpart.

ABSTRACT: Phthalocyanines possess unique optical and electronic properties and thus are widely used in (opto)electronic devices, coatings, photodynamic therapy, etc. Extension of their ?-electron systems could produce molecular materials with red-shifted absorption for a broader range of applications. However, access to expanded phthalocyanine analogues with more than four isoindoline units is challenging due to the limited synthetic possibilities. Here, we report the controlled on-surface synthesis of a gadolinium-supernaphthalocyanine macrocycle and its open-chain counterpart poly(benzodiiminoisoindoline) on a silver surface from a naphthalene dicarbonitrile precursor. Their formation is controlled by the on-surface high-dilution principle and steered by different metal templates, i.e., gadolinium atoms and the bare silver surface, which also act as oligomerization catalysts. By using scanning tunneling microscopy, photoemission spectroscopy, and density functional theory calculations, the chemical structures along with the mechanical and electronic properties of these phthalocyanine analogues with extended ?-conjugation are investigated in detail.

SUBMITTER: Fan Q

PROVIDER: S-EPMC6834595 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

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Template-controlled on-surface synthesis of a lanthanide supernaphthalocyanine and its open-chain polycyanine counterpart.

Fan Qitang Q Luy Jan-Niclas JN Liebold Martin M Greulich Katharina K Zugermeier Malte M Sundermeyer Jörg J Tonner Ralf R Gottfried J Michael JM

Nature communications 20191106 1

Phthalocyanines possess unique optical and electronic properties and thus are widely used in (opto)electronic devices, coatings, photodynamic therapy, etc. Extension of their π-electron systems could produce molecular materials with red-shifted absorption for a broader range of applications. However, access to expanded phthalocyanine analogues with more than four isoindoline units is challenging due to the limited synthetic possibilities. Here, we report the controlled on-surface synthesis of a ...[more]

PMID: 31695045

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Project description:Complexes featuring lanthanide (Ln)-Si bonds represent a highly neglected research area. Herein, we report a series of open-shell Ln(II+) and Ln(III+) complexes bearing ?-bonded silyl and base-stabilized N-heterocyclic silylene (NHSi) ligands. The reactions of the Ln(III+) complexes Cp3Ln (Ln = Tm, Ho, Tb, Gd; Cp = cyclopentadienide) with the 18-crown-6 (18-cr-6)-stabilized 1,4-oligosilanyl dianion [(18-cr-6)KSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2K(18-cr-6)] (1) selectively afford the corresponding metallacyclopentasilane salts [Cp2Ln({Si(SiMe3)2SiMe2}2)](-)[K2(18-cr-6)2Cp](+) [Ln = Tm (2a), Ho (2b), Tb (2c), Gd (2d)]. Complexes 2a-2d represent the first examples of structurally characterized Tm, Ho, Tb, and Gd complexes featuring Ln-Si bonds. Strikingly, the analogous reaction of 1 with the lighter element analogue Cp3Ce affords the acyclic product [Cp3CeSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2-Cp3Ce](2-)2[K(18-cr-6)](+) (3) as the first example of a complex featuring a Ce-Si bond. In an alternative synthetic approach, the aryloxy-functionalized benzamidinato NHSi ligand Si(OC6H4-2-tBu){(NtBu)2CPh} (4a) and the alkoxy analogue Si(OtBu){(NtBu)2CPh} (4b) were reacted with Cp*2Sm(OEt2), affording, by OEt2 elimination, the corresponding silylene complexes, both featuring Sm(II+) centers: Cp*2Sm ? :Si(O-C6H4-2-tBu){(NtBu)2CPh} (6) and Cp*2Sm ? :Si(OtBu){(NtBu)2CPh} (5). Complexes 5 and 6 are the first four-coordinate silylene complexes of any f-block element to date. All complexes were fully characterized by spectroscopic means and by single-crystal X-ray diffraction analysis. In the series 2a-2d, a linear correlation was observed between the Ln-Si bond lengths and the covalent radii of the corresponding Ln metals. Moreover, in complexes 5 and 6, notably long Sm-Si bonds are observed, in accordance with a donor-acceptor interaction between Si and Sm [5, 3.4396(15) Å; 6, 3.3142(18) Å]. Density functional theory calculations were carried out for complexes 2a-2d, 5, and 6 to elucidate the bonding situation between the Ln(II+) or Ln(III+) centers and Si. In particular, a decrease in the Mayer bond order (MBO) of the Ln-Si bond is observed in the series 2a-2d in moving from the lighter to the heavier lanthanides (Tm = 0.53, Ho = 0.62, Tb = 0.65, and Gd = 0.75), which might indicate decreasing covalency in the Ln-Si bond. In accordance with the long bond lengths observed experimentally in complexes 5 and 6, comparatively low MBOs were determined for both silylene complexes (5, 0.24; 6, 0.25) .

Dataset Information

Template-controlled on-surface synthesis of a lanthanide supernaphthalocyanine and its open-chain polycyanine counterpart.

Publications

Template-controlled on-surface synthesis of a lanthanide supernaphthalocyanine and its open-chain polycyanine counterpart.

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