5 Multicomponent Self-Assembly . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
5.1 Platinum-Pyridyl-Carboxylate Multicomponent Assembly . . . . . . . . . . . . . . . . . . . . . . . . . 241
5.2 Prismatic Metallacages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . 241
5.3 Supramolecule-to-Supramolecule Transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
5.4 Post-Self-Assembly Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
6 Summary, Conclusion, and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
Abbreviations
4,4
0 -bipy 4,4
0 -Bipyridine
bzqn
7,8-Benzoquinoline
Cp
Cyclopentadienyl
DArF
N,N-Diarylformamidinate
dppp
Diphenylphosphinopropane
en
1,2-Diaminoethane
OTf
Triflate anion
SCC
Supramolecular coordination complex
thpy
2-(2-Thienyl)pyridine
UH
Uracil monoanion
1 Introduction
The motto “united we stand, divided we fall” has broad implications, resulting in its
widespread use in songs, public speeches, political movements, and popular
culture. Although attributed to Aesop (ca. sixth century BC) [1], nature has
ultimately championed this concept on the molecular level with many examples
of complex architectures that owe their syntheses and stabilities to the spontaneous
formation of weak, non-directional interactions. When these hydrogen bonds, van
der Waals interactions, etc. work in concert to adjoin multiple molecular building
blocks, fascinating examples of complexity, symmetry, and function result, oftentimes unparalleled and irreproducible in the laboratory. Singularly, these bonds are
easily ruptured, with hydrogen bonds providing a mere 4–5 kcal mol
–1 of stabilization per instance. Van der Waals interactions, encompassing Keesom, Debye, and
London dispersion forces, are even weaker still. Yet, when the 500,000 to 2.5
million hydrogen bonds of an exemplary macromolecule such as human genomic
DNA are considered in aggregate, the resulting species is greatly stabilized by these
interactions that are pauce in strength but not in number. Likewise, the myriad van
der Waals interactions between a surface and the spatulae projecting from the
footpads of gecko lizards provides the sole attractive force by which these creatures
adhere to a number of materials – a fascinating example of the collective robustness
of seemingly trivial molecular interactions [2].
Whereas natural systems are advantaged by millions of years of evolution,
providing biosynthetic routes to carefully control and organize weak interactions
that are otherwise difficult to direct, scientists can exploit materials and conditions
230
T.R. Cook and P.J. Stang
5.1 Platinum-Pyridyl-Carboxylate Multicomponent Assembly . . . . . . . . . . . . . . . . . . . . . . . . . 241
5.2 Prismatic Metallacages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . 241
5.3 Supramolecule-to-Supramolecule Transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
5.4 Post-Self-Assembly Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
6 Summary, Conclusion, and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
Abbreviations
4,4
0 -bipy 4,4
0 -Bipyridine
bzqn
7,8-Benzoquinoline
Cp
Cyclopentadienyl
DArF
N,N-Diarylformamidinate
dppp
Diphenylphosphinopropane
en
1,2-Diaminoethane
OTf
Triflate anion
SCC
Supramolecular coordination complex
thpy
2-(2-Thienyl)pyridine
UH
Uracil monoanion
1 Introduction
The motto “united we stand, divided we fall” has broad implications, resulting in its
widespread use in songs, public speeches, political movements, and popular
culture. Although attributed to Aesop (ca. sixth century BC) [1], nature has
ultimately championed this concept on the molecular level with many examples
of complex architectures that owe their syntheses and stabilities to the spontaneous
formation of weak, non-directional interactions. When these hydrogen bonds, van
der Waals interactions, etc. work in concert to adjoin multiple molecular building
blocks, fascinating examples of complexity, symmetry, and function result, oftentimes unparalleled and irreproducible in the laboratory. Singularly, these bonds are
easily ruptured, with hydrogen bonds providing a mere 4–5 kcal mol
–1 of stabilization per instance. Van der Waals interactions, encompassing Keesom, Debye, and
London dispersion forces, are even weaker still. Yet, when the 500,000 to 2.5
million hydrogen bonds of an exemplary macromolecule such as human genomic
DNA are considered in aggregate, the resulting species is greatly stabilized by these
interactions that are pauce in strength but not in number. Likewise, the myriad van
der Waals interactions between a surface and the spatulae projecting from the
footpads of gecko lizards provides the sole attractive force by which these creatures
adhere to a number of materials – a fascinating example of the collective robustness
of seemingly trivial molecular interactions [2].
Whereas natural systems are advantaged by millions of years of evolution,
providing biosynthetic routes to carefully control and organize weak interactions
that are otherwise difficult to direct, scientists can exploit materials and conditions
230
T.R. Cook and P.J. Stang