What does a single exclamation mark do in YAML?

That ! is the non-specific tag.

The YAML specification 1.2 (as well as the previous 1.1) says that :

By explicitly specifying a “!” non-specific tag property, the node would then be resolved to a “vanilla” sequence, mapping, or string, according to its kind.

Take a look here to the tag "grammar":

none    : Unspecified tag (automatically resolved by application).
'!'     : Non-specific tag (by default, "!!map"/"!!seq"/"!!str").
'!foo'  : Primary (by convention, means a local "!foo" tag).
'!!foo' : Secondary (by convention, means "tag:yaml.org,2002:foo").
'!h!foo': Requires "%TAG !h! <prefix>" (and then means "<prefix>foo").
'!<foo>': Verbatim tag (always means "foo").

Why is YamlDotNet throwing a error? I can't be 100% sure, but I think you found a bug.

YamlDotNet is a port of LibYAML, so it's easy to compare sources.

Line 2635 of scanner.c (LibYAML):

/* Check if the tag is non-empty. */
if (!length) {

Line 2146 of Scanner.cs (YamlDotNet ):

// Check if the tag is non-empty.
if (tag.Length == 0)

I know, both looks very similar, but at this point length is 1 and tag.Length is 0. Original C code takes care of the initial "!" (whole length) but C# doesn't do it (just the tag "name" length).

File an issue to the project.