Inclusion of Chloranil in a Layered Double Hydroxide

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Accommodating Unwelcome Guests in Inorganic Layered Hosts: Inclusion of Chloranil in a Layered

Double Hydroxide

Dipak Dutta and Sukumaran Vasudevan*

Department of Inorganic and Physical Chemistry,

Indian Institute of Science, Bangalore 560012, India

Supporting Information

Figure S1. TGA profiles of (a) Mg-Al LDH-AB, (b) Mg-Al LDH-(AB∙p-chloranil) and (c) Mg-Al LDH-(AB∙o-chloranil). The para-chloranil to AB molar ratio is 0.81 and ortho-chloranil to AB is 0.45.

The weight loss below 250 ºC was used to estimate the water content.

Figure S2. Calculated Mulliken charges on individual atoms of the (a) p-aminobenzoate anion, (b) para-chloranil and (c) ortho-chloranil molecules.

Table S1. Infrared and Raman band positions and assignments for Mg-Al LDH-AB and potassium p- aminobenzoate.

Table S2. Infrared and Raman band positions and assignments for Mg-Al LDH-(AB∙p-chloranil).

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Figure S1. TGA profiles of (a) Mg-Al LDH-AB, (b) Mg-Al LDH-(AB∙p-chloranil) and (c) Mg-Al LDH-(AB∙o-chloranil). The para-chloranil to AB molar ratio is 0.81 and ortho-chloranil to AB is 0.45.

The weight loss below 250ºC was used to estimate the water content.

100 200 300 400 500 600 700 800 900 60

80 100

(c) (b)

% Weight loss

Temperature (⁰C)

(a)

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(a) (b)

(c)

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Table S1. Infrared and Raman band positions (cm^-1) and assignments for Mg-Al LDH-AB and potassium p-aminobenzoate.

Infrared Raman Assignment Potassium p-

aminobenzoate Mg-Al LDH-AB

Potassium p-

aminobenzoate Mg-Al LDH-AB 3383

3370 3227 ---- ---- 1606 1591 1530

1395

1285

1174

1136 1084 859

---- ----

3385 3350 3217 ---- ---- 1611 1592 1528

1397

1281

1176

1139 1093 857

673 444

3337 ---- 3228 3062 3015 ---- 1606 1520

1395

1283

1179

1139 ---- 855

640 ----

3319 ---- 3206 3062 3014 ---- 1607 1521

1391

1277

1182

1140 ---- 852

640 ----

ν_asym(NH₂) ν(OH) νsymm(NH2) ν( Aromatic C-H) ν(Aromatic C-H) νasym(Aromatic C-C) δ(N-H)

ν_asym(COO^-) and νsymm(Aromatic C-C) νsymm(COO^-)

ν(C-N)

δ(N-H) and δ(C-H) (out-of- plane) for p-disubstituted benzene δ(C-H)

δ(C-H) (in-plane)

δ(C-H) (out-of-plane) for p- disubstituted benzene

Benzene ring vibration δ(Layer O-H)

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Table S2. Infrared and Raman band positions (cm^-1) and assignments for Mg-Al LDH-(AB∙p-chloranil).

Infrared Raman Assignment 3385

3350 3217 ---- ---- ---- 1611 1592 ---- 1528

1397 ---- 1281 ---- 1176

1139 1093 ----

857

3335 --- 3219 3063 3015 1643 ---- 1606 1588 1517

1391 1311 1278 1245 1180

1140 ---- 997

852

ν_asym(NH₂) ν(OH) νsymm(NH2) ν(Aromatic C-H) ν(Aromatic C-H) ν(C=O) of chloranil νasym(Aromatic C-C) δ(N-H)

ν(C=C) of chloranil

νsymm(Aromatic C-C) and νasym(COO^-)

νsymm(COO^-)

ν(C-C) of chloranil ν(C-N)

ν(C-Cl) of chloranil

δ(N-H) and δ(C-H) (out-of-plane) for p-disubstituted benzene

δ(C-H)

(C-H) (in-plane) ν(C-Cl) of chloranil

Benzene ring vibration

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Table S3. Infrared and Raman band positions (cm^-1) and assignments for Mg-Al LDH-(AB∙o- chloranil).

Infrared Raman Assignment 3385

3350 3217 ---- ---- ---- 1611 1592 ---- 1528 1397 1281 ---- 1176

1139 1093 ---- 857

673 444

3335 ---- 3219 3063 3015 1637 ---- 1606 1562 1519 1391 1278 1248 1182

1142 ---- 989 852

640 ----

ν_asym(NH₂) ν(OH) νsymm(NH2) ν(Aromatic C-H) ν(Aromatic C-H) ν(C=O) of chloranil νasym(Aromatic C-C) δ(N-H)

ν(C=C) of chloranil

νsymm(Aromatic C-C) and νasym(COO^-) ν_symm(COO^-)

ν(C-N)

ν(C-Cl) of chloranil

δ(C-H)

(C-H) (in-plane) ν(C-Cl) of chloranil

Benzene ring vibration δ(Layer O-H)

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Figure S3. Variation of the interlayer spacing of Mg-Al LDH-(AB·chloranil) with increasing chloranil:AB molar ratio as obtained from MD simulations.

0.0 0.2 0.4 0.6 0.8 1.0

5 10 15 20 25

para-chloranil ortho-chloranil

Interlayer spacing

chloranil/AB