Anion binding by metallo-receptors of 5,5′-dicarbamate-2,2′- bipyridine ligands

Biao Wu; Jin Yang; Xiaojuan Huang; Shaoguang Li; Chuandong Jia; Xiao Juan Yang; Ning Tang; Christoph Janiak

doi:10.1039/c0dt01561j

Anion binding by metallo-receptors of 5,5′-dicarbamate-2,2′- bipyridine ligands

Biao Wu^*
, Jin Yang
, Xiaojuan Huang
, Shaoguang Li
, Chuandong Jia
, Xiao Juan Yang
, Ning Tang
, Christoph Janiak

^*Corresponding author for this work

Northwest University China
Lanzhou University
CAS - Lanzhou Institute of Chemical Physics
Heinrich Heine University Düsseldorf

Research output: Contribution to journal › Article › peer-review

15 Citations (Scopus)

Abstract

Three 5,5′-dicarbamate-2,2′-bipyridine ligands (L = L ¹-L³) bearing ethyl, isopropyl or tert-butyl terminals, respectively, on the carbamate substituents were synthesized. Reaction of the ligands L with the transition metal ions M = Fe²⁺, Cu²⁺, Zn²⁺ or Ru²⁺ gave the complexes ML_nX ₂·xG (1-12, n = 1-3; X = Cl, NO₃, ClO₄, BF₄, PF₆, SO₄; G = Et₂O, DMSO, CH₃OH, H₂O), of which [Fe(L²) ₃⊃SO₄]·8.5H₂O (2), [Fe(L ¹)₃⊃(BF₄)₂]·2CH ₃OH (7), [Fe(L²)₃⊃(Et₂O) ₂](BF₄)₂·2CH₃OH (8), [ZnCl₂(L¹)][ZnCl₂(L¹)(DMSO)] ·2DMSO (9), [Zn(L¹)₃⊃(NO₃) ₂]·2H₂O (10), [Zn(L²) ₃⊃(ClO₄)(Et₂O)]ClO₄· Et₂O·2CH₃OH·1.5H₂O (11), and [Cu(L¹)₂(DMSO)](ClO₄)₂·2DMSO (12) were elucidated by single-crystal X-ray crystallography. In the complexes ML_nX₂·xG the metal ion is coordinated by n = 1, 2 or 3 chelating bipyridine moieties (with other anionic or solvent ligands for n = 1 and 2) depending on the transition metal and reaction conditions. Interestingly, the carbamate functionalities are involved in hydrogen bonding with various guests (anions or solvents), especially in the tris(chelate) complexes which feature the well-organized C₃-clefts for effective guest inclusion. Moreover, the anion binding behavior of the pre-organized tris(chelate) complexes was investigated in solution by fluorescence titration using the emissive [RuL₃]²⁺ moiety as a probe. The results show that fluorescent recognition of anion in solution can be achieved by the Ru^II complexes which exhibit good selectivities for SO ₄^2-.

Original language	English
Pages (from-to)	5687-5696
Number of pages	10
Journal	Dalton Transactions
Volume	40
Issue number	21
DOIs	https://doi.org/10.1039/c0dt01561j
Publication status	Published - 7 Jun 2011
Externally published	Yes

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@article{393149a5b8354f84aa37d7ed1cfd267f,

title = "Anion binding by metallo-receptors of 5,5′-dicarbamate-2,2′- bipyridine ligands",

abstract = "Three 5,5′-dicarbamate-2,2′-bipyridine ligands (L = L 1-L3) bearing ethyl, isopropyl or tert-butyl terminals, respectively, on the carbamate substituents were synthesized. Reaction of the ligands L with the transition metal ions M = Fe2+, Cu2+, Zn2+ or Ru2+ gave the complexes MLnX 2·xG (1-12, n = 1-3; X = Cl, NO3, ClO4, BF4, PF6, SO4; G = Et2O, DMSO, CH3OH, H2O), of which [Fe(L2) 3⊃SO4]·8.5H2O (2), [Fe(L 1)3⊃(BF4)2]·2CH 3OH (7), [Fe(L2)3⊃(Et2O) 2](BF4)2·2CH3OH (8), [ZnCl2(L1)][ZnCl2(L1)(DMSO)] ·2DMSO (9), [Zn(L1)3⊃(NO3) 2]·2H2O (10), [Zn(L2) 3⊃(ClO4)(Et2O)]ClO4· Et2O·2CH3OH·1.5H2O (11), and [Cu(L1)2(DMSO)](ClO4)2·2DMSO (12) were elucidated by single-crystal X-ray crystallography. In the complexes MLnX2·xG the metal ion is coordinated by n = 1, 2 or 3 chelating bipyridine moieties (with other anionic or solvent ligands for n = 1 and 2) depending on the transition metal and reaction conditions. Interestingly, the carbamate functionalities are involved in hydrogen bonding with various guests (anions or solvents), especially in the tris(chelate) complexes which feature the well-organized C3-clefts for effective guest inclusion. Moreover, the anion binding behavior of the pre-organized tris(chelate) complexes was investigated in solution by fluorescence titration using the emissive [RuL3]2+ moiety as a probe. The results show that fluorescent recognition of anion in solution can be achieved by the RuII complexes which exhibit good selectivities for SO 42-.",

author = "Biao Wu and Jin Yang and Xiaojuan Huang and Shaoguang Li and Chuandong Jia and Yang, \{Xiao Juan\} and Ning Tang and Christoph Janiak",

year = "2011",

month = jun,

day = "7",

doi = "10.1039/c0dt01561j",

language = "English",

volume = "40",

pages = "5687--5696",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Anion binding by metallo-receptors of 5,5′-dicarbamate-2,2′- bipyridine ligands

AU - Wu, Biao

AU - Yang, Jin

AU - Huang, Xiaojuan

AU - Li, Shaoguang

AU - Jia, Chuandong

AU - Yang, Xiao Juan

AU - Tang, Ning

AU - Janiak, Christoph

PY - 2011/6/7

Y1 - 2011/6/7

N2 - Three 5,5′-dicarbamate-2,2′-bipyridine ligands (L = L 1-L3) bearing ethyl, isopropyl or tert-butyl terminals, respectively, on the carbamate substituents were synthesized. Reaction of the ligands L with the transition metal ions M = Fe2+, Cu2+, Zn2+ or Ru2+ gave the complexes MLnX 2·xG (1-12, n = 1-3; X = Cl, NO3, ClO4, BF4, PF6, SO4; G = Et2O, DMSO, CH3OH, H2O), of which [Fe(L2) 3⊃SO4]·8.5H2O (2), [Fe(L 1)3⊃(BF4)2]·2CH 3OH (7), [Fe(L2)3⊃(Et2O) 2](BF4)2·2CH3OH (8), [ZnCl2(L1)][ZnCl2(L1)(DMSO)] ·2DMSO (9), [Zn(L1)3⊃(NO3) 2]·2H2O (10), [Zn(L2) 3⊃(ClO4)(Et2O)]ClO4· Et2O·2CH3OH·1.5H2O (11), and [Cu(L1)2(DMSO)](ClO4)2·2DMSO (12) were elucidated by single-crystal X-ray crystallography. In the complexes MLnX2·xG the metal ion is coordinated by n = 1, 2 or 3 chelating bipyridine moieties (with other anionic or solvent ligands for n = 1 and 2) depending on the transition metal and reaction conditions. Interestingly, the carbamate functionalities are involved in hydrogen bonding with various guests (anions or solvents), especially in the tris(chelate) complexes which feature the well-organized C3-clefts for effective guest inclusion. Moreover, the anion binding behavior of the pre-organized tris(chelate) complexes was investigated in solution by fluorescence titration using the emissive [RuL3]2+ moiety as a probe. The results show that fluorescent recognition of anion in solution can be achieved by the RuII complexes which exhibit good selectivities for SO 42-.

AB - Three 5,5′-dicarbamate-2,2′-bipyridine ligands (L = L 1-L3) bearing ethyl, isopropyl or tert-butyl terminals, respectively, on the carbamate substituents were synthesized. Reaction of the ligands L with the transition metal ions M = Fe2+, Cu2+, Zn2+ or Ru2+ gave the complexes MLnX 2·xG (1-12, n = 1-3; X = Cl, NO3, ClO4, BF4, PF6, SO4; G = Et2O, DMSO, CH3OH, H2O), of which [Fe(L2) 3⊃SO4]·8.5H2O (2), [Fe(L 1)3⊃(BF4)2]·2CH 3OH (7), [Fe(L2)3⊃(Et2O) 2](BF4)2·2CH3OH (8), [ZnCl2(L1)][ZnCl2(L1)(DMSO)] ·2DMSO (9), [Zn(L1)3⊃(NO3) 2]·2H2O (10), [Zn(L2) 3⊃(ClO4)(Et2O)]ClO4· Et2O·2CH3OH·1.5H2O (11), and [Cu(L1)2(DMSO)](ClO4)2·2DMSO (12) were elucidated by single-crystal X-ray crystallography. In the complexes MLnX2·xG the metal ion is coordinated by n = 1, 2 or 3 chelating bipyridine moieties (with other anionic or solvent ligands for n = 1 and 2) depending on the transition metal and reaction conditions. Interestingly, the carbamate functionalities are involved in hydrogen bonding with various guests (anions or solvents), especially in the tris(chelate) complexes which feature the well-organized C3-clefts for effective guest inclusion. Moreover, the anion binding behavior of the pre-organized tris(chelate) complexes was investigated in solution by fluorescence titration using the emissive [RuL3]2+ moiety as a probe. The results show that fluorescent recognition of anion in solution can be achieved by the RuII complexes which exhibit good selectivities for SO 42-.

UR - https://www.scopus.com/pages/publications/79957471857

U2 - 10.1039/c0dt01561j

DO - 10.1039/c0dt01561j

M3 - Article

C2 - 21327244

AN - SCOPUS:79957471857

SN - 1477-9226

VL - 40

SP - 5687

EP - 5696

JO - Dalton Transactions

JF - Dalton Transactions

IS - 21

ER -

Anion binding by metallo-receptors of 5,5′-dicarbamate-2,2′- bipyridine ligands

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