12 research outputs found
Induction and Rationalization of Supramolecular Chirality in the Tweezer–Diamine Complexes: Insights from Experimental and DFT Studies
A series of supramolecular chiral
1:1 sandwich complexes (<b>1</b><sub>M</sub>·L and <b>2</b><sub>M</sub>·L) consisting of diphenylether/ethane bridged
metallobisporphyrin host (<b>1</b><sub>M</sub> and <b>2</b><sub>M</sub>; M: Zn/Mg) and chiral diamine guest (L) have been presented.
The host–guest complexes are compared just upon changing the
metal ion (Mg vs Zn) or the bridge (highly flexible ethane vs rigid
diphenylether) keeping other factors similar. The factors that would
influence the chirality induction process along with their contributions
toward the sign and intensity of the CD couplet of the overall complex
have been analyzed. Larger CD amplitude was observed in the host–guest
complex with the more flexible ethane bridge as compared to the rigid
diphenylether bridged one, irrespective of the metal ion used. Also,
Zn complexes have displayed larger CD amplitude because of their stronger
binding with the chiral diamines. A fairly linear dependence between
the binding constant (<i>K</i>) and CD amplitude has been
observed. Moreover, the amplitude of the CD couplet has been correlated
with the relative steric bulk of the substituent at the stereogenic
center: with increasing the bulk, CD intensity gradually increases.
However, large increase of steric hindrance, after a threshold value,
has diminished the intensity. The observation of a weak positive CD
couplet between (1<i>R</i>,2<i>R</i>)-DPEA guest
and Zn-bisporphyrin hosts indicates that the clockwise-twisted (steric-controlled)
conformer is more populated as compared to the anticlockwise (chirality-controlled)
one. In contrast, amplitude of the positive CD couplets is larger
with Mg-bisporphyrin hosts, suggesting almost exclusive contribution
of the clockwise-twisted conformer guided solely by sterics. DFT calculations
support the experimental observations and have displayed the possible
interconversion between clockwise and anticlockwise twisted conformers
just upon changing the bulk of the substituent irrespective of the
nature of chirality at the stereogenic center
Synthesis, Structure, and Properties of a Series of Chiral Tweezer–Diamine Complexes Consisting of an Achiral Zinc(II) Bisporphyrin Host and Chiral Diamine Guest: Induction and Rationalization of Supramolecular Chirality
We report here the synthesis, structure,
and spectroscopic properties of a series of supramolecular chiral
1:1 tweezer–diamine complexes consisting of an achiral Zn(II)
bisporphyrin (Zn<sub>2</sub>DPO) host and five different chiral diamine
guests, namely, (<i>R</i>)-diaminopropane (DAP), (1<i>S</i>,2<i>S</i>)-diaminocyclohexane (CHDA), (<i>S</i>)-phenylpropane diamine (PPDA), (<i>S</i>)-phenyl
ethylenediamine (PEDA), and (1<i>R</i>,2<i>R</i>)-diphenylethylene diamine (DPEA). The solid-state structures are
preserved in solution, as reflected in their <sup>1</sup>H NMR spectra,
which also revealed the remarkably large upfield shifts of the N<i>H</i><sub>2</sub> guest protons with the order Zn<sub>2</sub>DPO·DAP > Zn<sub>2</sub>DPO·CHDA > Zn<sub>2</sub>DPO·PPDA> Zn<sub>2</sub>DPO·PEDA ≫ Zn<sub>2</sub>DPO·DPEA, which happens to be the order of binding constants
of the respective diamines with Zn<sub>2</sub>DPO. As the bulk of
the substituent at the chiral center of the guest ligand increases,
the Zn–N<sub>ax</sub> distance of the tweezer–diamine
complex also increases, which eventually lowers the binding of the
guest ligand toward the host. Also, the angle between the two porphyrin
rings gradually increases with increasing bulk of the guest in order
to accommodate the guest within the bisporphyrin cavity with minimal
steric clash. The notably high amplitude bisignate CD signal response
by Zn<sub>2</sub>DPO·DAP, Zn<sub>2</sub>DPO·CHDA, and Zn<sub>2</sub>DPO·PPDA can be ascribed to the complex’s high
stability and the formation of a unidirectional screw as observed
in the X-ray structures of the complexes. A relatively lower value
of CD amplitude shown by Zn<sub>2</sub>DPO·PEDA is due to the
lower stability of the complex. The projection of the diamine binding
sites of the chiral guest would make the two porphyrin macrocycles
oriented in either a clockwise or anticlockwise direction in order
to minimize host–guest steric clash. In sharp contrast, Zn<sub>2</sub>DPO·DPEA shows a very low amplitude bisignate CD signal
due to the presence of both left- (dictated by the pre-existing chirality
of (1<i>R</i>,2<i>R</i>)-DPEA) and right-handed
screws (dictated by the steric differentiation at the chiral center)
of the molecule, as evident from X-ray crystallography. The present
work demonstrates a full and unambiguous rationalization of the observed
chirality transfer processes from the chiral guest to the achiral
host
Induction and Rationalization of Supramolecular Chirality in the Tweezer–Diamine Complexes: Insights from Experimental and DFT Studies
A series of supramolecular chiral
1:1 sandwich complexes (<b>1</b><sub>M</sub>·L and <b>2</b><sub>M</sub>·L) consisting of diphenylether/ethane bridged
metallobisporphyrin host (<b>1</b><sub>M</sub> and <b>2</b><sub>M</sub>; M: Zn/Mg) and chiral diamine guest (L) have been presented.
The host–guest complexes are compared just upon changing the
metal ion (Mg vs Zn) or the bridge (highly flexible ethane vs rigid
diphenylether) keeping other factors similar. The factors that would
influence the chirality induction process along with their contributions
toward the sign and intensity of the CD couplet of the overall complex
have been analyzed. Larger CD amplitude was observed in the host–guest
complex with the more flexible ethane bridge as compared to the rigid
diphenylether bridged one, irrespective of the metal ion used. Also,
Zn complexes have displayed larger CD amplitude because of their stronger
binding with the chiral diamines. A fairly linear dependence between
the binding constant (<i>K</i>) and CD amplitude has been
observed. Moreover, the amplitude of the CD couplet has been correlated
with the relative steric bulk of the substituent at the stereogenic
center: with increasing the bulk, CD intensity gradually increases.
However, large increase of steric hindrance, after a threshold value,
has diminished the intensity. The observation of a weak positive CD
couplet between (1<i>R</i>,2<i>R</i>)-DPEA guest
and Zn-bisporphyrin hosts indicates that the clockwise-twisted (steric-controlled)
conformer is more populated as compared to the anticlockwise (chirality-controlled)
one. In contrast, amplitude of the positive CD couplets is larger
with Mg-bisporphyrin hosts, suggesting almost exclusive contribution
of the clockwise-twisted conformer guided solely by sterics. DFT calculations
support the experimental observations and have displayed the possible
interconversion between clockwise and anticlockwise twisted conformers
just upon changing the bulk of the substituent irrespective of the
nature of chirality at the stereogenic center
Induction and Rationalization of Supramolecular Chirality in the Tweezer–Diamine Complexes: Insights from Experimental and DFT Studies
A series of supramolecular chiral
1:1 sandwich complexes (<b>1</b><sub>M</sub>·L and <b>2</b><sub>M</sub>·L) consisting of diphenylether/ethane bridged
metallobisporphyrin host (<b>1</b><sub>M</sub> and <b>2</b><sub>M</sub>; M: Zn/Mg) and chiral diamine guest (L) have been presented.
The host–guest complexes are compared just upon changing the
metal ion (Mg vs Zn) or the bridge (highly flexible ethane vs rigid
diphenylether) keeping other factors similar. The factors that would
influence the chirality induction process along with their contributions
toward the sign and intensity of the CD couplet of the overall complex
have been analyzed. Larger CD amplitude was observed in the host–guest
complex with the more flexible ethane bridge as compared to the rigid
diphenylether bridged one, irrespective of the metal ion used. Also,
Zn complexes have displayed larger CD amplitude because of their stronger
binding with the chiral diamines. A fairly linear dependence between
the binding constant (<i>K</i>) and CD amplitude has been
observed. Moreover, the amplitude of the CD couplet has been correlated
with the relative steric bulk of the substituent at the stereogenic
center: with increasing the bulk, CD intensity gradually increases.
However, large increase of steric hindrance, after a threshold value,
has diminished the intensity. The observation of a weak positive CD
couplet between (1<i>R</i>,2<i>R</i>)-DPEA guest
and Zn-bisporphyrin hosts indicates that the clockwise-twisted (steric-controlled)
conformer is more populated as compared to the anticlockwise (chirality-controlled)
one. In contrast, amplitude of the positive CD couplets is larger
with Mg-bisporphyrin hosts, suggesting almost exclusive contribution
of the clockwise-twisted conformer guided solely by sterics. DFT calculations
support the experimental observations and have displayed the possible
interconversion between clockwise and anticlockwise twisted conformers
just upon changing the bulk of the substituent irrespective of the
nature of chirality at the stereogenic center
Building-up Remarkably Stable Magnesium Porphyrin Polymers Self-Assembled via Bidentate Axial Ligands: Synthesis, Structure, Surface Morphology, and Effect of Bridging Ligands
A series of supramolecular architectures of magnesium
tetranitrooctaethylporphyrins
mediated by several bidentate axial ligands have been synthesized
in excellent yields and structurally characterized. Six conjugated
axial ligand with increasing chain lengths have been utilized in the
present investigations in which the Mg···Mg nonbonding
distance between successive ions also increases from 0.73 to 2.70
nm in the series. To the best of our knowledge, this is the first
report where stable metallo-porphyrin polymers with such long spacers
have been synthesized in one pot so easily. Linear one-dimensional
(1D) polymeric chains were observed in the X-ray structure of the
six-coordinated complexes in which porphyrin units are aligned parallel
to each other to have so-called “shish kebab” like architectures
to maintain offset-stacked overlap. However, after an optimum Mg···Mg
nonbonding distance, these 1D chain do not continue, rather they form
five-coordinated porphyrin dimers with “wheel-and-axle”
like architectures which are then self-aggregated by π–π
interactions in a perpendicular manner to fill space created by large
bridging ligands more effectively which consequently results in spherical
structures. The structures of the molecules in solution and their
surface patterns on highly ordered pyrolytic graphite (HOPG) have
also been investigated
Highly Enhanced Bisignate Circular Dichroism of Ferrocene-Bridged Zn(II) Bisporphyrin <i>Tweezer</i> with Extended Chiral Substrates due to Well-Matched Host–Guest System
Four
new chiral <i>tweezer-</i>diamine complexes, consisting
of an achiral ferrocene-bridged Zn(II)bisporhyrin host (<b>1</b>) and two small diamines (1<i>R</i>,2<i>R</i>)-1,2-diphenylethylene diamine {(1<i>R</i>,2<i>R</i>)-DPEA} and (1<i>S</i>,2<i>S</i>)-1,2-cyclohexane
diamine {(1<i>S</i>,2<i>S</i>)-CHDA} and two extended
diamines (1<i>R</i>,2<i>R</i>)-<i>N</i>,<i>N</i>′-bis-(isonicotinoyl)-1,2-diphenylethylene
diamine {(1<i>R</i>,2<i>R</i>)-DPEApy} and (1<i>S</i>,2<i>S</i>)-<i>N</i>,<i>N</i>′-bis-(isonicotinoyl)-1,2-cyclohexane diamine {(1<i>S</i>,2<i>S</i>)-CHDApy} chiral guests, are reported. Additions
of (1<i>R</i>,2<i>R</i>)-DPEA and (1<i>S</i>,2<i>S</i>)-CHDA separately to <b>1</b> in dichloromethane
result in the formation of 1:1 sandwich complexes <b>1·</b>DPEA<sub>(<i>R</i>,<i>R</i>)</sub> and <b>1·</b>CHDA<sub>(<i>S</i>,<i>S</i>)</sub>, respectively, at low guest concentration and 1:2 anti complexes <b>1·</b>(DPEA<sub>(<i>R</i>,<i>R</i>)</sub>)<sub>2</sub> and <b>1·</b>(CHDA<sub>(<i>S</i>,<i>S</i>)</sub>)<sub>2</sub>, respectively, at higher
guest concentration. In contrast, separate additions of (1<i>R</i>,2<i>R</i>)-DPEApy and (1<i>S</i>,2<i>S</i>)-CHDApy to <b>1</b> produce only 1:1 sandwich complexes
of <b>1·</b>DPEApy<sub>(<i>R</i>,<i>R</i>)</sub> and <b>1·</b>CHDApy<sub>(<i>S</i>,<i>S</i>)</sub>, respectively. The binding constants at 295 K between <b>1</b> and (1<i>R</i>,2<i>R</i>)-DPEA are observed
to be (4.7 ± 0.2) × 10<sup>4</sup> M<sup>–1</sup> and (4.3 ± 0.3) × 10<sup>3</sup> M<sup>–1</sup> for 1:1 sandwich and 1:2 anti form, respectively, while the respective
values with (1<i>S</i>,2<i>S</i>)-CHDA are (1.5
± 0.2) × 10<sup>5</sup> M<sup>–1</sup> and (5.9 ±
0.3) × 10<sup>3</sup> M<sup>–1</sup>. However, much larger
values of (2.5 ± 0.3) × 10<sup>5</sup> M<sup>–1</sup> and (1.3 ± 0.3) × 10<sup>6</sup> M<sup>–1</sup> have been observed with DPEApy<sub>(<i>R</i>,<i>R</i>)</sub> and CHDApy<sub>(<i>S</i>,<i>S</i>)</sub>, respectively, to produce the corresponding 1:1 sandwich complexes. <b>1·</b>DPEApy<sub>(<i>R</i>,<i>R</i>)</sub> (<i>A</i><sub>cal</sub>, −1759 cm<sup>–1</sup> M<sup>–1</sup>) (<i>A</i><sub>cal</sub> = Δε<sub>1</sub> – Δε<sub>2</sub>, representing the total
amplitude of the calculated circular dichroism (CD) couplets) shows
∼10-fold increase in CD amplitude compared to the values observed
for <b>1·</b>DPEA<sub>(<i>R</i>,<i>R</i>)</sub> (<i>A</i><sub>cal</sub>, +187 cm<sup>–1</sup> M<sup>–1</sup>), while <b>1·</b>CHDApy<sub>(<i>S</i>,<i>S</i>)</sub> (<i>A</i><sub>cal</sub>, +1886 cm<sup>–1</sup> M<sup>–1</sup>) shows nearly
3-fold increase of the CD amplitude compared to the value observed
for <b>1·</b>CHDA<sub>(<i>S</i>,<i>S</i>)</sub> (<i>A</i><sub>cal</sub>, −785 cm<sup>–1</sup> M<sup>–1</sup>) at 295 K. The <i>A</i><sub>cal</sub> values of −1759 cm<sup>–1</sup> M<sup>–1</sup> and +1886 cm<sup>–1</sup> M<sup>–1</sup> observed
for the <b>1·</b>DPEApy<sub>(<i>R</i>,<i>R</i>)</sub> and <b>1·</b>CHDApy<sub>(<i>S</i>,<i>S</i>)</sub>, respectively, are extremely high. To
the best of our knowledge, these are some of the largest values reported
for a chirality induction process involving bisporphyrin <i>tweezer</i> receptors. The large enhancement in the CD signal intensity is due
to the well complementarity size between Zn(II)bisporphyrin host and
the extended chiral diamines guest, which results large unidirectional
twisting of two porphyrin units to accommodate the guests having preorganized
binding sites with minimum host–guest steric interactions.
It is interesting to note that <b>1·</b>DPEA<sub>(<i>R</i>,<i>R</i>)</sub> and <b>1·</b>DPEApy<sub>(<i>R</i>,<i>R</i>)</sub> show CD signal opposite
in sign to each other, which happens to be the case between <b>1·</b>CHDA<sub>(<i>S</i>,<i>S</i>)</sub> and <b>1·</b>CHDApy<sub>(<i>S</i>,<i>S</i>)</sub> also
A Nonempirical Approach for Direct Determination of the Absolute Configuration of 1,2-Diols and Amino Alcohols Using Mg(II)bisporphyrin
We
report here a simple, facile, and direct nonempirical protocol
for determining the absolute stereochemistry of a variety of chiral
1,2-diols and amino alcohols at room temperature with no chemical
derivatization using Mg(II)bisporphyrin as a host. Addition of excess
substrates resulted in the formation of a 1:2 host–guest complex
in which two substrates bind in an unusual <i>endo-endo</i> fashion because of interligand H-bonding within the bisporphyrin
cavity leading to the formation of a unidirectional screw in the bisporphyrin
moiety that allowed us an accurate absolute stereochemical determination
of the chiral substrate via exciton-coupled circular dichroism (ECCD).
The sign of the CD couplet has also been found to be inverted when
the stereogenic center is moved by one C atom simply from the bound
to an unbound functionality and thus able to discriminate between
them successfully. Strong complexation of the alcoholic oxygen with
Mg(II)bisporphyrin rigidifies the host–guest complex, which
eventually enhances its ability to stereochemically differentiate
the asymmetric center. The ECCD sign of a large number of substrates
has followed consistent and predictable trends; thus, the system is
widely applicable. Moreover, computational calculations clearly support
the experimental observations along with the absolute stereochemistry
of the chiral substrate
A Nonempirical Approach for Direct Determination of the Absolute Configuration of 1,2-Diols and Amino Alcohols Using Mg(II)bisporphyrin
We
report here a simple, facile, and direct nonempirical protocol
for determining the absolute stereochemistry of a variety of chiral
1,2-diols and amino alcohols at room temperature with no chemical
derivatization using Mg(II)bisporphyrin as a host. Addition of excess
substrates resulted in the formation of a 1:2 host–guest complex
in which two substrates bind in an unusual <i>endo-endo</i> fashion because of interligand H-bonding within the bisporphyrin
cavity leading to the formation of a unidirectional screw in the bisporphyrin
moiety that allowed us an accurate absolute stereochemical determination
of the chiral substrate via exciton-coupled circular dichroism (ECCD).
The sign of the CD couplet has also been found to be inverted when
the stereogenic center is moved by one C atom simply from the bound
to an unbound functionality and thus able to discriminate between
them successfully. Strong complexation of the alcoholic oxygen with
Mg(II)bisporphyrin rigidifies the host–guest complex, which
eventually enhances its ability to stereochemically differentiate
the asymmetric center. The ECCD sign of a large number of substrates
has followed consistent and predictable trends; thus, the system is
widely applicable. Moreover, computational calculations clearly support
the experimental observations along with the absolute stereochemistry
of the chiral substrate
Highly Enhanced Bisignate Circular Dichroism of Ferrocene-Bridged Zn(II) Bisporphyrin <i>Tweezer</i> with Extended Chiral Substrates due to Well-Matched Host–Guest System
Four
new chiral <i>tweezer-</i>diamine complexes, consisting
of an achiral ferrocene-bridged Zn(II)bisporhyrin host (<b>1</b>) and two small diamines (1<i>R</i>,2<i>R</i>)-1,2-diphenylethylene diamine {(1<i>R</i>,2<i>R</i>)-DPEA} and (1<i>S</i>,2<i>S</i>)-1,2-cyclohexane
diamine {(1<i>S</i>,2<i>S</i>)-CHDA} and two extended
diamines (1<i>R</i>,2<i>R</i>)-<i>N</i>,<i>N</i>′-bis-(isonicotinoyl)-1,2-diphenylethylene
diamine {(1<i>R</i>,2<i>R</i>)-DPEApy} and (1<i>S</i>,2<i>S</i>)-<i>N</i>,<i>N</i>′-bis-(isonicotinoyl)-1,2-cyclohexane diamine {(1<i>S</i>,2<i>S</i>)-CHDApy} chiral guests, are reported. Additions
of (1<i>R</i>,2<i>R</i>)-DPEA and (1<i>S</i>,2<i>S</i>)-CHDA separately to <b>1</b> in dichloromethane
result in the formation of 1:1 sandwich complexes <b>1·</b>DPEA<sub>(<i>R</i>,<i>R</i>)</sub> and <b>1·</b>CHDA<sub>(<i>S</i>,<i>S</i>)</sub>, respectively, at low guest concentration and 1:2 anti complexes <b>1·</b>(DPEA<sub>(<i>R</i>,<i>R</i>)</sub>)<sub>2</sub> and <b>1·</b>(CHDA<sub>(<i>S</i>,<i>S</i>)</sub>)<sub>2</sub>, respectively, at higher
guest concentration. In contrast, separate additions of (1<i>R</i>,2<i>R</i>)-DPEApy and (1<i>S</i>,2<i>S</i>)-CHDApy to <b>1</b> produce only 1:1 sandwich complexes
of <b>1·</b>DPEApy<sub>(<i>R</i>,<i>R</i>)</sub> and <b>1·</b>CHDApy<sub>(<i>S</i>,<i>S</i>)</sub>, respectively. The binding constants at 295 K between <b>1</b> and (1<i>R</i>,2<i>R</i>)-DPEA are observed
to be (4.7 ± 0.2) × 10<sup>4</sup> M<sup>–1</sup> and (4.3 ± 0.3) × 10<sup>3</sup> M<sup>–1</sup> for 1:1 sandwich and 1:2 anti form, respectively, while the respective
values with (1<i>S</i>,2<i>S</i>)-CHDA are (1.5
± 0.2) × 10<sup>5</sup> M<sup>–1</sup> and (5.9 ±
0.3) × 10<sup>3</sup> M<sup>–1</sup>. However, much larger
values of (2.5 ± 0.3) × 10<sup>5</sup> M<sup>–1</sup> and (1.3 ± 0.3) × 10<sup>6</sup> M<sup>–1</sup> have been observed with DPEApy<sub>(<i>R</i>,<i>R</i>)</sub> and CHDApy<sub>(<i>S</i>,<i>S</i>)</sub>, respectively, to produce the corresponding 1:1 sandwich complexes. <b>1·</b>DPEApy<sub>(<i>R</i>,<i>R</i>)</sub> (<i>A</i><sub>cal</sub>, −1759 cm<sup>–1</sup> M<sup>–1</sup>) (<i>A</i><sub>cal</sub> = Δε<sub>1</sub> – Δε<sub>2</sub>, representing the total
amplitude of the calculated circular dichroism (CD) couplets) shows
∼10-fold increase in CD amplitude compared to the values observed
for <b>1·</b>DPEA<sub>(<i>R</i>,<i>R</i>)</sub> (<i>A</i><sub>cal</sub>, +187 cm<sup>–1</sup> M<sup>–1</sup>), while <b>1·</b>CHDApy<sub>(<i>S</i>,<i>S</i>)</sub> (<i>A</i><sub>cal</sub>, +1886 cm<sup>–1</sup> M<sup>–1</sup>) shows nearly
3-fold increase of the CD amplitude compared to the value observed
for <b>1·</b>CHDA<sub>(<i>S</i>,<i>S</i>)</sub> (<i>A</i><sub>cal</sub>, −785 cm<sup>–1</sup> M<sup>–1</sup>) at 295 K. The <i>A</i><sub>cal</sub> values of −1759 cm<sup>–1</sup> M<sup>–1</sup> and +1886 cm<sup>–1</sup> M<sup>–1</sup> observed
for the <b>1·</b>DPEApy<sub>(<i>R</i>,<i>R</i>)</sub> and <b>1·</b>CHDApy<sub>(<i>S</i>,<i>S</i>)</sub>, respectively, are extremely high. To
the best of our knowledge, these are some of the largest values reported
for a chirality induction process involving bisporphyrin <i>tweezer</i> receptors. The large enhancement in the CD signal intensity is due
to the well complementarity size between Zn(II)bisporphyrin host and
the extended chiral diamines guest, which results large unidirectional
twisting of two porphyrin units to accommodate the guests having preorganized
binding sites with minimum host–guest steric interactions.
It is interesting to note that <b>1·</b>DPEA<sub>(<i>R</i>,<i>R</i>)</sub> and <b>1·</b>DPEApy<sub>(<i>R</i>,<i>R</i>)</sub> show CD signal opposite
in sign to each other, which happens to be the case between <b>1·</b>CHDA<sub>(<i>S</i>,<i>S</i>)</sub> and <b>1·</b>CHDApy<sub>(<i>S</i>,<i>S</i>)</sub> also
A Nonempirical Approach for Direct Determination of the Absolute Configuration of 1,2-Diols and Amino Alcohols Using Mg(II)bisporphyrin
We
report here a simple, facile, and direct nonempirical protocol
for determining the absolute stereochemistry of a variety of chiral
1,2-diols and amino alcohols at room temperature with no chemical
derivatization using Mg(II)bisporphyrin as a host. Addition of excess
substrates resulted in the formation of a 1:2 host–guest complex
in which two substrates bind in an unusual <i>endo-endo</i> fashion because of interligand H-bonding within the bisporphyrin
cavity leading to the formation of a unidirectional screw in the bisporphyrin
moiety that allowed us an accurate absolute stereochemical determination
of the chiral substrate via exciton-coupled circular dichroism (ECCD).
The sign of the CD couplet has also been found to be inverted when
the stereogenic center is moved by one C atom simply from the bound
to an unbound functionality and thus able to discriminate between
them successfully. Strong complexation of the alcoholic oxygen with
Mg(II)bisporphyrin rigidifies the host–guest complex, which
eventually enhances its ability to stereochemically differentiate
the asymmetric center. The ECCD sign of a large number of substrates
has followed consistent and predictable trends; thus, the system is
widely applicable. Moreover, computational calculations clearly support
the experimental observations along with the absolute stereochemistry
of the chiral substrate