PMID- 18642933
OWN - NLM
STAT- MEDLINE
DCOM- 20090318
LR  - 20240402
IS  - 1520-4898 (Electronic)
IS  - 0001-4842 (Print)
IS  - 0001-4842 (Linking)
VI  - 41
IP  - 12
DP  - 2008 Dec
TI  - Heteroligated supramolecular coordination complexes formed via the halide-induced 
      ligand rearrangement reaction.
PG  - 1618-29
LID - 10.1021/ar800025w [doi]
AB  - Supramolecular coordination chemistry allows researchers to synthesize 
      higher-order structures that approach the nanoscale dimensions of small enzymes. 
      Frequently, such structures have highly symmetric macrocyclic square or cage 
      shapes. To build functional structures that mimic the complex recognition, 
      catalytic, and allosteric properties of enzymes, researchers must do more than 
      synthesize highly symmetric nanoscale structures. They must also simultaneously 
      incorporate different functionalities into these structures and learn how to 
      regulate their relative arrangement with respect to each other. Designing such 
      heteroligated coordination complexes remains a significant challenge for 
      supramolecular chemists. This Account focuses on the discovery and development of 
      a novel supramolecular reaction known as the halide-induced ligand rearrangement 
      (HILR) reaction. Two hemilabile ligands with different binding strengths combine 
      with d(8) transition metal precursors that contain halide ions. The reaction 
      spontaneously results in heteroligated complexes and is highly modular and 
      general. Indeed, it not only can be used to prepare tweezer complexes but also 
      allows for the rapid and quantitative formation of heteroligated macrocyclic 
      triple-decker/step and rectangular box complexes from a variety of different 
      ligands and transition metal ions. The relative arrangement between functional 
      groups A and B in these structures can be regulated in situ using small ancillary 
      ligands such as halides, CO, and nitriles. Based on this reaction, zinc- and 
      magnesium-porphyrin moieties can be incorporated into heteroligated macrocyclic 
      or tweezer scaffolds. These examples demonstrate the convergent and cofacial 
      assembly of functional sites that are known to be involved in numerous processes 
      in enzymes. They also show how the relative spatial and lateral distances of 
      these sites can be varied, in many cases reversibly. Researchers can use such 
      complexes to study a wide range of enzymatic processes, including catalysis, 
      molecular recognition, electron transfer, and allosteric signal transfer.
FAU - Oliveri, Christopher G
AU  - Oliveri CG
AD  - Department of Chemistry and the International Institute for Nanotechnology, 
      Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, USA.
FAU - Ulmann, Pirmin A
AU  - Ulmann PA
FAU - Wiester, Michael J
AU  - Wiester MJ
FAU - Mirkin, Chad A
AU  - Mirkin CA
LA  - eng
GR  - DP1 OD000285/OD/NIH HHS/United States
PT  - Journal Article
PT  - Research Support, N.I.H., Extramural
PT  - Research Support, U.S. Gov't, Non-P.H.S.
PL  - United States
TA  - Acc Chem Res
JT  - Accounts of chemical research
JID - 0157313
RN  - 0 (Enzymes)
RN  - 0 (Ligands)
RN  - 0 (Macrocyclic Compounds)
RN  - 0 (Porphyrins)
RN  - 2683-84-3 (chlorin)
SB  - IM
MH  - Catalysis
MH  - Crystallography, X-Ray
MH  - Enzymes/chemical synthesis/*chemistry
MH  - Ligands
MH  - Macrocyclic Compounds/chemistry
MH  - Models, Molecular
MH  - Molecular Mimicry
MH  - Porphyrins/chemistry
MH  - Stereoisomerism
PMC - PMC8191499
MID - NIHMS1709535
EDAT- 2008/07/23 09:00
MHDA- 2009/03/19 09:00
PMCR- 2021/06/10
CRDT- 2008/07/23 09:00
PHST- 2008/07/23 09:00 [pubmed]
PHST- 2009/03/19 09:00 [medline]
PHST- 2008/07/23 09:00 [entrez]
PHST- 2021/06/10 00:00 [pmc-release]
AID - 10.1021/ar800025w [doi]
PST - ppublish
SO  - Acc Chem Res. 2008 Dec;41(12):1618-29. doi: 10.1021/ar800025w.