Table 3.

Summary of NMR interaction studies between porphyrins and cyclodextrins.

Porphyrin (Guest)	Macromolecule (Host)	NMR Technique	Result	Ref
TPPS4	α-, β-, γ-CD	1H NMR chem. shift perturbation of host 2D 1H1H ROESY of host–guest mixture	2:1 (CD:TPPS4) inclusion complexes with β- and γ-CD, no complex with α-CD β-CD: through secondary face γ -CD: through primary face	[176]
TPPS4, Mn(III)TPPS4	α-, β-, γ-CD	1H and 13C NMR chem. shift perturbation of host 2D 1H1H ROESY of host–guest mixture	Strongest binding for β-CD	[177]
Zn(II)TPPS4	β-CD	1H NMR chem. shift perturbation of host	Formation of inclusion complex	[178]
Zn(II)TPPS4 Pd(II)TPPS4 TPPC4	β-, γ-CD HP-β-CD HP-γ-CD	1H and 13C NMR chem. shift perturbation of host 2D 1H1H ROESY of host–guest mixture	Formation of inclusion complexes: (HP)β-CD: through secondary face (HP)γ -CD: through primary face Weak binding to CD exterior	[179]
TPPS4 TPPOC3PSa TPPC4 TPPOC3Py	β-Cd TMe-β-CD	1H and 13C NMR chem. shift perturbation of host 2D 1H1H ROESY 1H NMR spectral appearance of guest 13C-T1 relaxation time of host and guest	β-CD, TMe-β-CD: anionic porphyrin guests binding more favorable than cationic Disaggregation; formation of trans-type 2:1 complexes with TMe-β-CD TPPS4: stronger binding to TMe-β-CD than to β-CD Motional restriction of CD and TPP-phenyl rings (less pronounced inside cavity)	[180]
TPPS4 Acidic conditions	β-CD Me-β-CD HP-β-CD	1H and 13C NMR chem. shift perturbation of host 2D 1H1H ROESY 1H NMR spectral appearance of guest	β-CD, HP-β-CD: inclusion via secondary face Me-β-CD: inclusion via primary face Disaggregation of J-aggregates upon complexation	[181]
TPPS4 TPPS3 TPPS2o TPPS2a TMPyP	β-, γ-CD	1H NMR spectral appearance of guest 1H NMR chem. shift perturbation of host 2D 1H1H ROESY	Inclusion complexes formed with all but TPPS2a and TMPyP TPPS4, TPPS3, TPPS2o: Partial disaggregation Sulfonatophenyl- but not phenyl-group included in the case of mixed substituents Inclusion via secondary face for β-CD and primary for γ-CD	[182]
TPPS4 TPPC4	CD dimers with flexible spacers	1H NMR spectral appearance of guest 1H NMR chem. shift perturbation of host	Adjacently (“syn”) and oppositely (“anti”) capped TPPS4	[183]
TMPyP TPPS4H22+	α-, β-, γ-Cd TMe-β-CD SO3-β-CD DiMeSO3-β-CD	1H NMR chem. shift perturbation of host 1H NMR spectral appearance of guest 1H NMR chem. shift titration with host 2D 1H1H ROESY	TMPyP: External binding to native CDs and TMe-β-CD TPPS4H22+: Inclusion with β-CD via secondary and with γ-CD via primary face Fast exchange between free/complex form	[184]
TEPyP	β-CD HP-β-CD SBE-CD	1H NMR chem. shift perturbation of host 1H NMR spectral appearance of guest 2D 1H1H ROESY	Inclusion with β-CD and HP-β-CD from the primary face	[185]
TMPyP	SBE-CD	1H NMR spectral appearance of guest	Complex formation with SBE-CD Fast exchange between free/complex form	[186]
PyTPP	β-CD Tme-β-CD	1H NMR chem. shift perturbation of host 1H NMR spectral appearance of guest	Inclusion with TMe-β-CD (from the primary face) but hardly with β-CD	[187]
TPyP	HP-β-CD Di-Me-β-Cd TMe-β-CD	1H NMR spectral appearance of guest 2D 1H1H NOESY	1:1 complex with TMe-β-CD from the secondary face	[188]
TPyP	TMe-β-CD	1H NMR spectral appearance of guest at different pH	1:2 (TPyP:CD) complex pH-dependent release (acidic condition)	[189]
TPP, TPPC4 THPPb, TAPPc TMeOPPd	TMe-β-CD	1H NMR spectral appearance of host–guest mixture	All form 1:2 (TPP:CD) inclusion complexes with TMe-β-CD	[190]
octa-arginine-TPP (R8-TPP)	TMe-β-CD	1H NMR chem. shift titration with host 1H NMR spectral appearance of guest 2D 1H1H ROESY	Trans-type 1:2 (TPP:CD) inclusion complex with the non-substituted phenyl groups via secondary face Slow free/complex exchange rate	[191]
TPPS4	ZnTPP- DAPM-β-CDe	1H NMR spectral appearance of host–guest mixture 2D 1H1H NOESY 1H-DOSY	ZnTPP- β-CD forms self-inclusion and inclusion complexes with TPPS4 yielding vesicles and networks	[195]
Mn(III)TPP PEGylated	bridged bis(TMe-β-CD)	2D 1H1H NOESY	Inclusion complexes, formation of supramolecular polymers	[196]
TPPS4	ZnTPP-, DAPM-β-CDe DAPM-TMe-β-CDe	1H NMR spectral appearance of host–guest mixture 2D 1H1H NOESY	ZnTPP- β-CD and -TMe-β-CD form self-inclusion and inclusion complexes; the latter are dissolved in favor of TPPS4 inclusion Formation of networks and nanorods	[197]

^a TPPOC3PS: p-phenyl-O-(CH₂)₃-p-phenyl-(SO₃)⁻-tetra-phenylporphyrin; ^b THPP: meso-tetrakis(4-hydroxyphenyl) porphyrin; ^c TAPP: meso-tetrakis(4-aminophenyl) porphyrin; ^d TMeOPP: meso-tetrakis(4-methoxyphenyl) porphyrin; ^e DAPM: 6-deoxy-6-azidopermethyl.