@article{
 title = {Engineering Orthogonality in Supramolecular Polymers: From Simple Scaffolds to Complex Materials},
 type = {article},
 year = {2014},
 identifiers = {[object Object]},
 keywords = {(pdscs)-s-ii pincer complexes,abc triblock copolymers,block-copolymers,chain functionalized polymers,chemistry,metal-coordination,molecular recognition,motifs,opening metathesis polymerization,ruthenium catalysts},
 pages = {2405-2416},
 volume = {47},
 websites = {<Go to ISI>://WOS:000340702000018\nhttp://pubs.acs.org/doi/pdfplus/10.1021/ar500128w},
 month = {8},
 publisher = {AMER CHEMICAL SOC},
 city = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA},
 id = {7240a07a-280f-3b23-b2c4-b6294bc6d231},
 created = {2015-12-14T19:51:25.000Z},
 file_attached = {false},
 profile_id = {3187ec9d-0fcc-3ba2-91e0-3075df9b18c3},
 group_id = {d75e47fd-ff52-3a4b-bf1e-6ebc7e454352},
 last_modified = {2017-03-14T12:30:08.401Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {ISI:000340702000018},
 source_type = {article},
 user_context = {Review},
 private_publication = {false},
 abstract = {CONSPECTUS: Owing to the mastery exhibited by Nature in integrating both
covalent and noncovalent interactions in a highly efficient manner, the
quest to construct polymeric systems that rival not only the precision
and fidelity but also the structure of natural systems has remained a
daunting challenge. Supramolecular chemists have long endeavored to
control the interplay between covalent and noncovalent bond formation,
so as to examine and fully comprehend how function is predicated on
self-assembly. The ability to reliably control polymer self-assembly is
essential to generate ``smart'' materials and has the potential to
tailor polymer properties (i.e., viscosity, electronic properties)
through fine-tuning the noncovalent interactions that comprise the
polymer architecture. In this context, supramolecular polymers have a
distinct advantage over fully covalent systems in that they are
dynamically modular, since noncovalent recognition motifs can be
engineered to either impart a desired functionality within the overall
architecture or provide a designed bias for the self-assembly process.
In this Account, we describe engineering principles being developed and
pursued by our group that exploit the orthogonal nature of noncovalent
interactions, such as hydrogen bonding, metal coordination, and
Coulombic interactions, to direct the self-assembly of functionalized
macromolecules, resulting in the formation of supramolecular polymers.
To begin, we describe our efforts to fabricate a modular
poly(norbornene)-based scaffold via ring-opening metathesis
polymerization (ROMP), wherein pendant molecular recognition elements
based upon nudeobase-mimicking elements (e.g., thymine, diaminotriazine)
or SCS-Pd-II pincer were integrated within covalent monofunctional or
symmetrically functionalized polymers. The simple polymer backbones
exhibited reliable self-assembly with complementary polymers or small
molecules. Within these systems, we applied successful protecting group
strategies and template polymerizations to enhance the control afforded
by ROMP. Main-chain-functionalized alternating block polymers based upon
SCS-Pd-II pincer-pyridine motifs were achieved through the combined
exploitation of bimetallic initiators and supramolecularly
functionalized terminators. Our initial design principles led to the
successful fabrication of both main-chain- and side-chain-functionalized
poly(norbornenes) via ROMP.
Utilizing all of these techniques in concert led to engineering
orthogonality while achieving complexity through the installation of
multiple supramolecular motifs within the side chain, main chain, or
both in our polymer systems. The exploitation and modification of design
principles based upon functional ROMP initiators and terminators has
resulted in the first synthesis of main-chain heterotelechelic polymers
that self-assemble into A/B/C supramolecular triblock polymers composed
of orthogonal cyanuric acid-Hamilton wedge and SCS-Pd-II pincer-pyridine
motifs. Furthermore, supramolecular A/B/A triblock copolymers were
realized through the amalgamation of functionalized monomers, ROMP
initiators, and terminators. To date, this ROMP-fabricated system
represents the only known method to afford polymer main chains and side
chains studded with orthogonal motifs. We end by discussing the impetus
to attain functional materials via orthogonal self-assembly.
Collectively, our studies suggest that combining covalent and
noncovalent bonds in a well-defined and precise manner is an essential
design element to achieve complex architectures. The results discussed
in this Account illustrate the finesse associated with engineering
orthogonal interactions within supramolecular systems and are considered
essential steps toward developing complex biomimetic materials with high
precision and fidelity.},
 bibtype = {article},
 author = {Elacqua, Elizabeth and Lye, Diane S and Weck, Marcus},
 journal = {ACCOUNTS OF CHEMICAL RESEARCH},
 number = {8}
}

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Supramolecular chemists have long endeavored to\ncontrol the interplay between covalent and noncovalent bond formation,\nso as to examine and fully comprehend how function is predicated on\nself-assembly. The ability to reliably control polymer self-assembly is\nessential to generate ``smart'' materials and has the potential to\ntailor polymer properties (i.e., viscosity, electronic properties)\nthrough fine-tuning the noncovalent interactions that comprise the\npolymer architecture. In this context, supramolecular polymers have a\ndistinct advantage over fully covalent systems in that they are\ndynamically modular, since noncovalent recognition motifs can be\nengineered to either impart a desired functionality within the overall\narchitecture or provide a designed bias for the self-assembly process.\nIn this Account, we describe engineering principles being developed and\npursued by our group that exploit the orthogonal nature of noncovalent\ninteractions, such as hydrogen bonding, metal coordination, and\nCoulombic interactions, to direct the self-assembly of functionalized\nmacromolecules, resulting in the formation of supramolecular polymers.\nTo begin, we describe our efforts to fabricate a modular\npoly(norbornene)-based scaffold via ring-opening metathesis\npolymerization (ROMP), wherein pendant molecular recognition elements\nbased upon nudeobase-mimicking elements (e.g., thymine, diaminotriazine)\nor SCS-Pd-II pincer were integrated within covalent monofunctional or\nsymmetrically functionalized polymers. The simple polymer backbones\nexhibited reliable self-assembly with complementary polymers or small\nmolecules. Within these systems, we applied successful protecting group\nstrategies and template polymerizations to enhance the control afforded\nby ROMP. Main-chain-functionalized alternating block polymers based upon\nSCS-Pd-II pincer-pyridine motifs were achieved through the combined\nexploitation of bimetallic initiators and supramolecularly\nfunctionalized terminators. Our initial design principles led to the\nsuccessful fabrication of both main-chain- and side-chain-functionalized\npoly(norbornenes) via ROMP.\nUtilizing all of these techniques in concert led to engineering\northogonality while achieving complexity through the installation of\nmultiple supramolecular motifs within the side chain, main chain, or\nboth in our polymer systems. The exploitation and modification of design\nprinciples based upon functional ROMP initiators and terminators has\nresulted in the first synthesis of main-chain heterotelechelic polymers\nthat self-assemble into A/B/C supramolecular triblock polymers composed\nof orthogonal cyanuric acid-Hamilton wedge and SCS-Pd-II pincer-pyridine\nmotifs. Furthermore, supramolecular A/B/A triblock copolymers were\nrealized through the amalgamation of functionalized monomers, ROMP\ninitiators, and terminators. To date, this ROMP-fabricated system\nrepresents the only known method to afford polymer main chains and side\nchains studded with orthogonal motifs. We end by discussing the impetus\nto attain functional materials via orthogonal self-assembly.\nCollectively, our studies suggest that combining covalent and\nnoncovalent bonds in a well-defined and precise manner is an essential\ndesign element to achieve complex architectures. The results discussed\nin this Account illustrate the finesse associated with engineering\northogonal interactions within supramolecular systems and are considered\nessential steps toward developing complex biomimetic materials with high\nprecision and fidelity.","bibtype":"article","author":"Elacqua, Elizabeth and Lye, Diane S and Weck, Marcus","journal":"ACCOUNTS OF CHEMICAL RESEARCH","number":"8","bibtex":"@article{\n title = {Engineering Orthogonality in Supramolecular Polymers: From Simple Scaffolds to Complex Materials},\n type = {article},\n year = {2014},\n identifiers = {[object Object]},\n keywords = {(pdscs)-s-ii pincer complexes,abc triblock copolymers,block-copolymers,chain functionalized polymers,chemistry,metal-coordination,molecular recognition,motifs,opening metathesis polymerization,ruthenium catalysts},\n pages = {2405-2416},\n volume = {47},\n websites = {<Go to ISI>://WOS:000340702000018\\nhttp://pubs.acs.org/doi/pdfplus/10.1021/ar500128w},\n month = {8},\n publisher = {AMER CHEMICAL SOC},\n city = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA},\n id = {7240a07a-280f-3b23-b2c4-b6294bc6d231},\n created = {2015-12-14T19:51:25.000Z},\n file_attached = {false},\n profile_id = {3187ec9d-0fcc-3ba2-91e0-3075df9b18c3},\n group_id = {d75e47fd-ff52-3a4b-bf1e-6ebc7e454352},\n last_modified = {2017-03-14T12:30:08.401Z},\n read = {false},\n starred = {false},\n authored = {false},\n confirmed = {true},\n hidden = {false},\n citation_key = {ISI:000340702000018},\n source_type = {article},\n user_context = {Review},\n private_publication = {false},\n abstract = {CONSPECTUS: Owing to the mastery exhibited by Nature in integrating both\ncovalent and noncovalent interactions in a highly efficient manner, the\nquest to construct polymeric systems that rival not only the precision\nand fidelity but also the structure of natural systems has remained a\ndaunting challenge. Supramolecular chemists have long endeavored to\ncontrol the interplay between covalent and noncovalent bond formation,\nso as to examine and fully comprehend how function is predicated on\nself-assembly. The ability to reliably control polymer self-assembly is\nessential to generate ``smart'' materials and has the potential to\ntailor polymer properties (i.e., viscosity, electronic properties)\nthrough fine-tuning the noncovalent interactions that comprise the\npolymer architecture. In this context, supramolecular polymers have a\ndistinct advantage over fully covalent systems in that they are\ndynamically modular, since noncovalent recognition motifs can be\nengineered to either impart a desired functionality within the overall\narchitecture or provide a designed bias for the self-assembly process.\nIn this Account, we describe engineering principles being developed and\npursued by our group that exploit the orthogonal nature of noncovalent\ninteractions, such as hydrogen bonding, metal coordination, and\nCoulombic interactions, to direct the self-assembly of functionalized\nmacromolecules, resulting in the formation of supramolecular polymers.\nTo begin, we describe our efforts to fabricate a modular\npoly(norbornene)-based scaffold via ring-opening metathesis\npolymerization (ROMP), wherein pendant molecular recognition elements\nbased upon nudeobase-mimicking elements (e.g., thymine, diaminotriazine)\nor SCS-Pd-II pincer were integrated within covalent monofunctional or\nsymmetrically functionalized polymers. The simple polymer backbones\nexhibited reliable self-assembly with complementary polymers or small\nmolecules. Within these systems, we applied successful protecting group\nstrategies and template polymerizations to enhance the control afforded\nby ROMP. Main-chain-functionalized alternating block polymers based upon\nSCS-Pd-II pincer-pyridine motifs were achieved through the combined\nexploitation of bimetallic initiators and supramolecularly\nfunctionalized terminators. Our initial design principles led to the\nsuccessful fabrication of both main-chain- and side-chain-functionalized\npoly(norbornenes) via ROMP.\nUtilizing all of these techniques in concert led to engineering\northogonality while achieving complexity through the installation of\nmultiple supramolecular motifs within the side chain, main chain, or\nboth in our polymer systems. The exploitation and modification of design\nprinciples based upon functional ROMP initiators and terminators has\nresulted in the first synthesis of main-chain heterotelechelic polymers\nthat self-assemble into A/B/C supramolecular triblock polymers composed\nof orthogonal cyanuric acid-Hamilton wedge and SCS-Pd-II pincer-pyridine\nmotifs. Furthermore, supramolecular A/B/A triblock copolymers were\nrealized through the amalgamation of functionalized monomers, ROMP\ninitiators, and terminators. To date, this ROMP-fabricated system\nrepresents the only known method to afford polymer main chains and side\nchains studded with orthogonal motifs. We end by discussing the impetus\nto attain functional materials via orthogonal self-assembly.\nCollectively, our studies suggest that combining covalent and\nnoncovalent bonds in a well-defined and precise manner is an essential\ndesign element to achieve complex architectures. The results discussed\nin this Account illustrate the finesse associated with engineering\northogonal interactions within supramolecular systems and are considered\nessential steps toward developing complex biomimetic materials with high\nprecision and fidelity.},\n bibtype = {article},\n author = {Elacqua, Elizabeth and Lye, Diane S and Weck, Marcus},\n journal = {ACCOUNTS OF CHEMICAL RESEARCH},\n number = {8}\n}","author_short":["Elacqua, E.","Lye, D., S.","Weck, M."],"urls":{"Website":"<Go to ISI>://WOS:000340702000018\\nhttp://pubs.acs.org/doi/pdfplus/10.1021/ar500128w"},"bibbaseid":"elacqua-lye-weck-engineeringorthogonalityinsupramolecularpolymersfromsimplescaffoldstocomplexmaterials-2014","role":"author","keyword":["(pdscs)-s-ii pincer complexes","abc triblock copolymers","block-copolymers","chain functionalized polymers","chemistry","metal-coordination","molecular recognition","motifs","opening metathesis polymerization","ruthenium catalysts"],"downloads":0},"search_terms":["engineering","orthogonality","supramolecular","polymers","simple","scaffolds","complex","materials","elacqua","lye","weck"],"keywords":["(pdscs)-s-ii pincer complexes","abc triblock copolymers","block-copolymers","chain functionalized polymers","chemistry","metal-coordination","molecular recognition","motifs","opening metathesis polymerization","ruthenium catalysts"],"authorIDs":[]}