robust photophysical properties, and excited state tuneability. It has now been
demonstrated that Ru(II)tris(2,2
0 -bipyridine) (RuBpy) can exhibit a templating effect
in the formation of the resultant metal organic framework (MOF) materials. A
number of new topologies have now been synthesized using Zn(II) ions and carboxylate ligands in which the encapsulated RuBpy clusters exhibit unique
photophysical properties. In this chapter, the relationship between MOF cavities
and the RuBpy photophysical properties is reviewed. Two polyhedral MOFs
(RuBpy@HKUST-1(Zn) and RuBpy@USF2) and five RuBpy templated MOFs
(RWLC-1,-2,-3,-5 and -6) are discussed in terms of cavity influence on excited
state population and decay pathways.
Keywords 2,2
0 -Bipyridine · Metal building block · Metal organic frameworks ·
Metal to ligand charge transfer states · Photophysics · Ruthenium(II) polyimines
Abbreviations
BDC
Benzene 1,4-dicarboxylate
BTCA Benzene-1,3,5 carboxylate
BTE
1,3,5-Tris(carboxyphenylethynyl)benzene
LF
Ligand field state
MBB
Metal building block
MLCT Metal to ligand charge transfer
MOF
Metal organic framework
POM
Polyoxometalate
RuBpy Ru(II)tris(2,2
0 -bipyridine)
RuBpy Ru(II)tris(2,2
0 -bipyridine)
TCPB
1,3,5-Tris(4-carboxyphenyl)benzene
1 Introduction
1.1 Metal Organic Frameworks
Metal organic frameworks (MOFs) constitute a class of functional porous materials
that provide an extensive foundation through which a wide range of applications can
be developed including, but not limited to, gas storage and separation, heterogeneous catalysis, drug delivery, sensors, environmental remediation, and light
harvesting [1–5]. The MOF class of materials feature high porosity, a wide array
of structural topologies, ease of synthesis, and tunable functionality [3, 6–8]. The
versatility of MOFs is due to the fact that these materials contain molecular building
blocks (MBBs) composed of metal coordination complexes linked through
multidentate organic ligands (Fig. 1) [9, 10]. The key advantage associated with
MOFs includes the fact that the geometry of the MBB can be tuned, the organic
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R. W. Larsen et al.
demonstrated that Ru(II)tris(2,2
0 -bipyridine) (RuBpy) can exhibit a templating effect
in the formation of the resultant metal organic framework (MOF) materials. A
number of new topologies have now been synthesized using Zn(II) ions and carboxylate ligands in which the encapsulated RuBpy clusters exhibit unique
photophysical properties. In this chapter, the relationship between MOF cavities
and the RuBpy photophysical properties is reviewed. Two polyhedral MOFs
(RuBpy@HKUST-1(Zn) and RuBpy@USF2) and five RuBpy templated MOFs
(RWLC-1,-2,-3,-5 and -6) are discussed in terms of cavity influence on excited
state population and decay pathways.
Keywords 2,2
0 -Bipyridine · Metal building block · Metal organic frameworks ·
Metal to ligand charge transfer states · Photophysics · Ruthenium(II) polyimines
Abbreviations
BDC
Benzene 1,4-dicarboxylate
BTCA Benzene-1,3,5 carboxylate
BTE
1,3,5-Tris(carboxyphenylethynyl)benzene
LF
Ligand field state
MBB
Metal building block
MLCT Metal to ligand charge transfer
MOF
Metal organic framework
POM
Polyoxometalate
RuBpy Ru(II)tris(2,2
0 -bipyridine)
RuBpy Ru(II)tris(2,2
0 -bipyridine)
TCPB
1,3,5-Tris(4-carboxyphenyl)benzene
1 Introduction
1.1 Metal Organic Frameworks
Metal organic frameworks (MOFs) constitute a class of functional porous materials
that provide an extensive foundation through which a wide range of applications can
be developed including, but not limited to, gas storage and separation, heterogeneous catalysis, drug delivery, sensors, environmental remediation, and light
harvesting [1–5]. The MOF class of materials feature high porosity, a wide array
of structural topologies, ease of synthesis, and tunable functionality [3, 6–8]. The
versatility of MOFs is due to the fact that these materials contain molecular building
blocks (MBBs) composed of metal coordination complexes linked through
multidentate organic ligands (Fig. 1) [9, 10]. The key advantage associated with
MOFs includes the fact that the geometry of the MBB can be tuned, the organic
156
R. W. Larsen et al.