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The Different Faces of 4′-Pyrimidinyl-Functionalized 4,2′:6′,4′′-Terpyridines: Metal–Organic Assemblies from Solution and on Au(111) and Cu(111) Surface Platforms

Nijs, Thomas and Klein, Y. Maximilian and Mousavi, S. Fatemeh and Ahsan, Aisha and Nowakowska, Sylwia and Constable, Edwin and Housecroft, Catherine and Jung, Thomas. (2018) The Different Faces of 4′-Pyrimidinyl-Functionalized 4,2′:6′,4′′-Terpyridines: Metal–Organic Assemblies from Solution and on Au(111) and Cu(111) Surface Platforms. Journal of the American Chemical Society, 140 (8). pp. 2933-2939.

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Abstract

A comparative investigation of crystal growth from solution and on-surface assembly in vacuo between copper and three 4'-(2-R-pyrimidin-5-yl)-4,2':6',4''-terpyridines with R = H (1), Me (2) or Et (3) is presented. In solution, ligand 3 combines with copper(II) acetate or copper(I) triflate in MeOH solution to give [Cu2(OAc)4(3)]n or {[Cu(3)(OMe)(MeOH)][CF3SO3].MeOH}n. In [Cu2(OAc)4(3)]n, paddle-wheel {Cu2(μ-OAc)4} nodes direct the assembly of 1D-zigzag chains which pack into 2D sheets. In {[Cu(3)(OMe)(MeOH)][CF3SO3].MeOH}n, the solvent is both a ligand and generates {Cu2(μ-OMe)2} units which function as planar 4-connecting nodes to generate a 2D (4,4) net with ligand 3. On Au(111) or Cu(111) surfaces in vacuo, no additional solvent or anions are involved in the assembly. The different substituents in 1, 2 or 3 allow precise molecular resolution imaging in scanning tunneling microscopy (STM). On Au(111), 1 and 2 assemble into close-packed assemblies, whilst 3 forms a regular porous network. The deposition of Cu ad-atoms results in reorganization leading to ladder-shaped surface metal-organic motifs. These on-surface coordination assemblies are independent of the 4'-substituent in the 4,2':6',4''-tpy and are reproduced on Cu(111) where Cu ad-atoms are available during the deposition and relaxation process at room temperature. Upon annealing at elevated temperatures, the original surface assemblies of 1 and 3 are modified and a transition from ladders into rhomboid structures is observed; for 2, a further quasi-hexagonal nanoporous network is observed.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
UniBasel Contributors:Housecroft, Catherine Elizabeth and Nijs, Thomas and Jung, Thomas A. and Klein, Maximilian and Mousavi, Seyedeh Fatemeh and Nowakowska, Sylwia and Ahsan, Aisha
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0002-7863
e-ISSN:1520-5126
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:12 Mar 2018 08:16
Deposited On:12 Mar 2018 08:15

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