DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Formation of a Fluorous/Organic Biphasic Supramolecular Octopus Assembly for Enhanced Porphyrin Phosphorescence in Air

Journal Article · · Angewandte Chemie International Edition (Online)
 [1];  [1];  [1];  [1];  [1];  [2];  [1]
  1. Univ. of North Texas, Denton, TX (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The trinuclear triangle-shaped system [tris{3,5-bis(heptafluoropropyl)-1,2,4-triazolatosilver(I)}] (1) and the multi-armed square-shaped metalloporphyrin PtOEP or the free porphyrin base H2OEP serve as excellent octopus hosts (OEP=2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine). Coupling of the fluorous/organic molecular octopi 1 and H2OEP or PtOEP by strong quadrupole-quadrupole and metal- interactions affords the supramolecular assemblies [1PtOEP] or [1H(2)OEP] (2a), which feature nanoscopic cavities surrounding the upper triangular and lower square cores. The fluorous/organic biphasic configuration of [1PtOEP] leads to an increase in the phosphorescence of PtOEP under ambient conditions. Guest molecules can be included in the biphasic double-octopus assembly in three different site-selective modes.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1335317
Journal Information:
Angewandte Chemie International Edition (Online), Vol. 54, Issue 16; ISSN 1521-3773
Publisher:
Gesselschaft Deutscher ChemikerCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

References (50)

Expected and Unconventional Ag+ Binding Modes in Heteronuclear Pt,Ag Coordination Polymers Derived from trans-[Pt(methylamine)2(pyrazole)2]2+ journal January 2012
Hydrothermal Chemistry of the Copper–Triazolate System: A Microporous Metal–Organic Framework Constructed from Magnetic {Cu3(μ3-OH)(triazolate)3}2+ Building Blocks, and Related Materials journal May 2006
Bioinspired Detection of Light Using a Porphyrin-Sensitized Single-Wall Nanotube Field Effect Transistor journal September 2006
Stacked Platinum Complexes of the Magnus’ Salt Type Inside a Coordination Cage journal January 2012
Remarkably Simple Fabrication of Superhydrophobic Surfaces Using Electroless Galvanic Deposition journal February 2007
Trinuclear Gold(I) Triazolates:  A New Class of Wide-Band Phosphors and Sensors journal August 2006
Functionalized Coordination Space in Metal-Organic Frameworks journal October 2008
Novel optical oxygen sensing material: platinum porphyrin-fluoropolymer film journal January 2000
Syntheses of macrocyclic enzyme models. 7. Octopus cyclophanes having L-aspartate residues as novel water-soluble hosts; aggregation behavior and induced-fit molecular recognition journal October 1990
Fluorous Metal−Organic Frameworks for High-Density Gas Adsorption journal December 2007
Engineering discrete stacks of aromatic molecules journal January 2009
A robust, porous, cationic silver(i) 3,5-diphenyl-1,2,4-triazolate framework with a uninodal 49.66 netElectronic supplementary information (ESI) available: experimental details, XPRD patterns, TGA curves and IR spectra. See http://www.rsc.org/suppdata/cc/b4/b404269g/ journal January 2004
Competing Supramolecular Interactions Give a New Twist to Terpyridyl Chemistry: Anion- and Solvent-Induced Formation of Spiral Arrays in Silver(I) Complexes of a Simple Terpyridine journal May 2002
Template-directed synthesis of donor/acceptor [2]catenanes and [2]rotaxanes journal January 2008
Octopus Molecules journal December 1974
High-efficiency organic electrophophorescent devices through balance of charge injection journal March 2002
Stable optical oxygen sensing materials based on click-coupling of fluorinated platinum(II) and palladium(II) porphyrins—A convenient way to eliminate dye migration and leaching journal July 2012
A Helical Metal−Metal Bonded Chain via the Pt→Ag Dative Bond journal January 2001
Dendrimer Chemistry book February 2009
Toluene-Sandwiched Trinuclear Copper(I) and Silver(I) Triazolates and Phosphine Adducts of Dinuclear Copper(I) and Silver(I) Triazolates journal May 2008
Crystallographic Observation of Dynamic Gas Adsorption Sites and Thermal Expansion in a Breathable Fluorous Metal-Organic Framework journal March 2009
Metal Azolate Frameworks: From Crystal Engineering to Functional Materials journal September 2011
Fluorous Pores in Coordination Networks journal October 2009
Krakenmoleküle journal December 1974
Supramolecular triangular and linear arrays of metal–radical solids using pyrazolato-silver( i ) motifs journal January 2004
Meniscus-climbing insects journal September 2005
Singlet–singlet excited-state absorption and triplet–triplet absorption of meso-tetraphenylporphine journal April 2000
First metal-encapsulating star polysulfoxide incorporating 2-amino-1,3,4-thiadiazole journal January 1997
Luminescence enhancement and tuning via multiple cooperative supramolecular interactions in an ion-paired multinuclear complex journal January 2011
Hydrothermal Chemistry of the Copper–Triazolate System: A Microporous Metal–Organic Framework Constructed from Magnetic {Cu3(μ3-OH)(triazolate)3}2+ Building Blocks, and Related Materials journal May 2006
Extrafluorescent electroluminescence in organic light-emitting devices journal April 2007
Funktionalisierter Koordinationsraum in metall-organischen Gerüsten journal October 2008
Solvothermal in Situ Metal/Ligand Reactions:  A New Bridge between Coordination Chemistry and Organic Synthetic Chemistry journal February 2007
Flexible Coordination Networks with Fluorinated Backbones. Remarkable Ability for Induced-Fit Enclathration of Organic Molecules journal March 2000
Fluorous Nanodroplets Structurally Confined in an Organopalladium Sphere journal September 2006
Photoconductive Liquid-Crystalline Derivatives of 6-Oxoverdazyl journal January 2012
Highly efficient phosphorescent emission from organic electroluminescent devices journal September 1998
Fluorous Metal–Organic Frameworks with Superior Adsorption and Hydrophobic Properties toward Oil Spill Cleanup and Hydrocarbon Storage journal November 2011
Supramolecular Chain Assemblies Formed by Interaction of a π Molecular Acid Complex of Mercury with π-Base Trinuclear Gold Complexes journal November 2000
Real-time monitoring of luminescent lifetime changes of PtOEP oxygen sensing film with LED/photodiode-based time-domain lifetime device journal January 2009
Remarkably Simple Fabrication of Superhydrophobic Surfaces Using Electroless Galvanic Deposition journal February 2007
Self-assembly of Ligands Designed for the Building of a New Type of [2 × 2] Metallic Grid. Anion Encapsulation and Diffusion NMR Spectroscopy journal January 2008
Stacked Platinum Complexes of the Magnus’ Salt Type Inside a Coordination Cage journal January 2012
High-efficiency fluorescent organic light-emitting devices using a phosphorescent sensitizer journal February 2000
Exceptionally Stable, Hollow Tubular Metal−Organic Architectures:  Synthesis, Characterization, and Solid-State Transformation Study journal March 2004
Organonitrile ligated silver complexes with perfluorinated weakly coordinating anions and their catalytic application for coupling reactions journal January 2005
Crystallographic Observation of Dynamic Gas Adsorption Sites and Thermal Expansion in a Breathable Fluorous Metal-Organic Framework journal March 2009
Solventless Supramolecular Chemistry via Vapor Diffusion of Volatile Small Molecules upon a New Trinuclear Silver(I)-Nitrated Pyrazolate Macrometallocyclic Solid: An Experimental/Theoretical Investigation of the Dipole/Quadrupole Chemisorption Phenomena journal November 2013
Solvothermal in situ Metal/Ligand Reactions: A New Bridge Between Coordination Chemistry and Organic Synthetic Chemistry journal May 2007
Dendrimer Chemistry book May 2020

Cited By (5)

Fluorous Metal–Organic Frameworks and Nonporous Coordination Polymers as Low‐κ Dielectrics journal August 2019
Photoluminescence Modulation in Lan­thanide(III)/Pyrazine-2,5-dicarboxylato/Nitrato Frameworks: Lanthanide(III)/Pyrazine-2,5-dicarboxylato/Nitrato Frameworks journal August 2015
The π-acidity/basicity of cyclic trinuclear units (CTUs): from a theoretical perspective to potential applications journal January 2019
Homoleptic Cyclic Trinuclear d 10 Complexes: from Self-Association via Metallophilic and Excimeric Bonding to the Breakage Thereof via Oxidative Addition, Dative Bonding, Quadrupolar, and Heterometal Bonding Interactions journal November 2019
Photoluminescence Modulation in Lan­thanide(III)/Pyrazine-2,5-dicarboxylato/Nitrato Frameworks journal September 2015


Figures / Tables (4)