Iron(II) bis(pyrazolyl)phenanthroline complexes as robust and efficient homogeneous catalysts for CO2-to-CO conversion under visible light

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This paper reports a family of homogeneous iron(II) bis(pyrazolyl)phenanthroline complexes, [Fe(bpzRphen)(H2O)2]X2 (Fe1–Fe4), for visible-light-driven CO2 reduction to CO using [Ru(bpy)3]2+ as photosensitizer and BIH as sacrificial electron donor in MeCN/H2O. All four complexes are active and selective for CO formation under 462 nm LED irradiation. Under the standard conditions (50 μM catalyst, 0.3 mM [Ru(bpy)3]2+, 0.11 M BIH, CO2-saturated MeCN/H2O, 308 K, 24 h), Fe2 gave the highest activity (TONCO = 1318, 84% CO selectivity), while Fe4 gave the highest selectivity in the series (TONCO = 1265, 91% CO selectivity). At lower Fe2 loading (3.12 μM), the system reached TONCO = 23,138 after 24 h and TONCO = 9754 after 4 h, with a total quantum yield of 8.24% reported in the abstract and 7.6% at 462 nm in the main text.

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	.	.	solvent A	.	.	.	.	.	.	λexc [nm]	.	TON CO	.	.	TON H2	.	.	.	.
1.	[[[Fe(bpzphen)(H2O)2](BF4)2 (Fe1) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		987			187					Property "Catalyst" (as page type) with input value "Fe(bpzphen)(H2O)2](BF4)2 (Fe1)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
2.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		1318			243					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
3.	[[[Fe(bpzPhphen)(H2O)2](ClO4)2 (Fe3) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		847			205					Property "Catalyst" (as page type) with input value "Fe(bpzPhphen)(H2O)2](ClO4)2 (Fe3)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
4.	[[[Fe(bpzCF3phen)(H2O)2](ClO4)2 (Fe4) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		1265			133					Property "Catalyst" (as page type) with input value "Fe(bpzCF3phen)(H2O)2](ClO4)2 (Fe4)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
5.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		311			51					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
6.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		1578			296					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
7.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		1593			300					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
8.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		2			22					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "" is not declared as a valid unit of measurement for this property.
9.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		1352			285					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
10.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		661			191					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
11.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		621			77					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
12.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	25.0 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		2086			123					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
13.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	12.5 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		4259			276					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
14.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	6.25 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		10			423.7 h-1					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
15.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	3.12 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		23			964.1 h-1					Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
16.	[[[Fe(bpzphen)(H2O)2](BF4)2 (Fe1) ]]	3.25 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)										Property "Catalyst" (as page type) with input value "Fe(bpzphen)(H2O)2](BF4)2 (Fe1)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35.
17.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	3.25 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)		9754								Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "%" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "absorbedphotonflux" is not declared as a valid unit of measurement for this property. "°C" can not be assigned to a declared number type with value 35. "h-1" is not declared as a valid unit of measurement for this property.
18.	[[[Fe(bpzPhphen)(H2O)2](ClO4)2 (Fe3) ]]	3.25 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)										Property "Catalyst" (as page type) with input value "Fe(bpzPhphen)(H2O)2](ClO4)2 (Fe3)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35.
19.	[[[Fe(bpzCF3phen)(H2O)2](ClO4)2 (Fe4) ]]	3.25 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	0.11 M			MeCN							462 nm (blue LED strip)										Property "Catalyst" (as page type) with input value "Fe(bpzCF3phen)(H2O)2](ClO4)2 (Fe4)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35.
20.	[[[Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2) ]]	50 μM	[[[Ru(bpy)3]2+ ]]	0.3 mM	BIH	27.5 mM			MeCN							462 nm (blue LED strip)		221								Property "Catalyst" (as page type) with input value "Fe(bpzMe2phen)(H2O)2](BF4)2 (Fe2)" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "μM" is not declared as a valid unit of measurement for this property. Property "Photosensitizer" (as page type) with input value "Ru(bpy)3]2+" contains invalid characters or is incomplete and therefore can cause unexpected results during a query or annotation process. "Molecule:" is not declared as a valid unit of measurement for this property. "CO2-saturated CO2" is not in the list (nitrogen, argon, CO2, CO, O2, H2, none) of allowed values for the "Feedstock gas" property. "°C" can not be assigned to a declared number type with value 35.

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